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.     

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。     

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.     

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.     

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.     

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.     

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.     

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.     

Effects of oxygen on the release and distribution of phosphorus in the sediments under the light condition

Effects of oxygen on the release and distribution of phosphorus (P) in the sediments in the presence of light were investigated, using sediment cores and overlying water from Lake Taihu, in China. The results show that P can be released from sediments to the overlying water in both anoxic and aerobic conditions. But more P was released in the anoxic condition. The transformation of P between various fractions in the sediments was observed during the release experiments. Concentrations of Ca-bound P and organic P in the sediments decreased in both conditions, but Fe/Al-bound P increased in the aerobic condition. The decrease of total P and P fractions in the sediments is consistent with the accumulative increase in quantity (AIQ) of total P (TP) in the overlying water, but is contrary with the AIQ of dissolved inorganic P. This is due to the uptake of algae by the dissolved inorganic P. Total nitrogen in the sediments in the anoxic condition was lower than that in the aerobic condition, and pH in the overlying water increased in the anoxic condition.     

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.     

Assessment of insecticide contamination in runoff and stream water of small agricultural streams in the main soybean area of Argentina

The first- and second-order streams, Brown and Horqueta, respectively, which are located in the main area of soybean production in Argentina were examined for insecticide contamination caused by runoff from nearby soybean fields. The insecticides most widely used in Argentina (chlorpyrifos, cypermethrin and endosulfan) were detected in sediments, suspended particles and water. Highest concentrations in suspended particles were 318 microg/kg for endosulfan in the stream Horqueta, while 226 microg/kg chlorpyrifos and 13.2 microg/kg cypermethrin were measured in the stream Brown. In the Horqueta stream 150 and 53 microg/kg chlorpyrifos and cypermethrin were detected in runoff sediments, respectively. Whereas cypermethrin concentrations in the suspended particles were relatively low, levels in the floodwater of Brown reached 0.7 microg/l. The highest chlorpyrifos concentration in floodwater was 0.45 microg/l in Brown. However, endosulfan was not detected in the water phase. In runoff water the highest concentrations measured were 0.3 microg/l for chlorpyrifos in Horqueta and 0.49 microg/l for cypermethrin in the Brown stream. On five sampling dates during the pesticide application period in Brown stream (2002/2003) the concentration of chlorpyrifos and cypermethrin in runoff and/or floodwater exceeded the water quality criteria for freshwater mentioned in this study. In three cases this insecticide concentration was measured in stream water, indicating an acute risk to aquatic life. The acute toxicity-exposure-ratio (TER) for chlorpyrifos and cypermethrin also shows an acute risk for aquatic invertebrates in the Brown stream. In the Horqueta chlorpyrifos concentrations in the runoff exceeded the safety levels three times during the application period (2001/2002), potentially endangering the aquatic fauna. Effects on aquatic macroinvertebrates after insecticide contamination were reported in earlier studies in Horqueta stream.     

Contamination status of arsenic and other trace elements in drinking water and residents from Tarkwa, a historic mining township in Ghana

This study was conducted to assess the contamination status of 22 trace elements, especially As in water and residents in Tarkwa, a historic mining town in Ghana. Drinking water and human urine samples were collected from Tarkwa in addition to control samples taken from Accra, the capital of Ghana in March, 2004. Concentrations of As and Mn in some drinking water samples from Tarkwa were found above the WHO drinking water guidelines posing a potential health risk for the people. A potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. No significant difference of As concentrations in human urine between mining town (Tarkwa) and control site (Accra) was observed. Although As concentrations in drinking water in Tarkwa were low, urinary As levels were comparable to those reported in highly As-affected areas in the world. These results suggest the presence of other sources of As contamination in Ghana. This is the first study on multi-elemental contamination in drinking water and human from a mining town in Ghana.     

Perfluorooctanesulfonate and perfluorooctanoate in raw and treated tap water from Osaka, Japan

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota, and humans. PFOS and PFOA have been detected in water in Japan. Nevertheless, occurrence of PFOS and PFOA in potable water from municipal water treatment plants is not clearly known. We analyzed PFOS and PFOA in raw and tap water samples collected from 14 drinking water treatment plants in winter and summer seasons in Osaka to determine the concentrations of PFOS and PFOA in raw and potable tap water samples. PFOS and PFOA were detected in all raw water samples. Concentration ranges of PFOS and PFOA in raw water were 0.26-22 ng/l and 5.2-92 ng/l, respectively. Whereas the concentrations PFOS in raw water from Osaka were similar to those in other areas in Japan, the concentrations of PFOA were higher than in other areas. Concentration ranges of PFOS and PFOA in potable tap water were 0.16-22 ng/l and 2.3-84 ng/l, respectively. There were positive correlations between PFC concentrations in raw water and tap water samples. Therefore, the removal efficiency of PFCs by the present water treatment may be low. Based on the current action value reported by U.S. Environmental Protection Agency, PFOA concentrations found in tap water in Osaka is not expected to pose health risks.     

Mercury methylation in aquatic systems affected by acid deposition

Recently, it has been noted that fish in acidified lakes may contain elevated levels of mercury. While there is correlation among lakes between depressed pH and high mercury concentrations in fish, the cause of this problem is unknown. A number of hypotheses have been advanced in explanation, including increased mercury deposition, changes in mercury mobility due to acidification, pH dependent changes in mercury uptake by biota, and alterations in population size and/or structure which result in increased bioaccumulation in fish. Because fish accumulate mercury mainly in an organic form, methylmercury, changes in the biogeochemical cycling of this compound might account for elevated bioaccumulation. Mercury methylation is predominantly a microbial process which occurs in situ in lakes. This review focuses on microbiological and biogeochemical changes that may lead to increased levels of methylmercury in fresh waters impacted by acid-deposition. In particular, we focus on the hypothesis that sulfate-reducing bacteria are important mediators of metal methylation in aquatic systems and, moreover, that sulfate-deposition may stimulate methylmercury production by enhancing the activity of sulfate-reducing bacteria in sediments.     

我国环境介质中多环芳烃的分布及其生态风险

持久性有机污染物多环芳烃(PAHs)在我国环境介质中广泛分布,美国EPA规定的16种.优先控制多环芳烃大多在我国大气、水体、沉积物、土壤和生物体内检出.总结了我国环境介质中PAHs污染水平及特点,分析了其存在的环境风险.我国大气中PAHs污染较重,尤其是北方.水体已普遍受PAHs污染,其中部分水体污染严重;沉积物多环芳烃污染大多处于低生态风险水平,但沉积记录研究表明有越来越严重的趋势.我国土壤和生物体PAHs含量较低,污染生态风险较小.部分区域蔬菜中PAHs含量较高,存在不可忽视的生态风险.     

Hexazinone and simazine dissipation in forestry field nurseries

Hexazinone and simazine field dissipation was studied in two different soils from Spain (Toledo and Burgos), devoted to forest nurseries for Pinus nigra. Laboratory experiments (adsorption-desorption isotherms, leaching experiment and degradation study) were carried out to determine possible mechanisms of dissipation. Higher adsorption was observed for hexazinone in Toledo (KfT = 0.69) compare to in Burgos soil (KfB = 0.20) probably due to the higher organic matter (OM) content of Toledo soil. No differences in adsorption were obtained for simazine in both soils (KfT = 1.27; KfB = 1.34). In every case, adsorption was higher for simazine than for hexazinone, in both soils. The total recovery of hexazinone in the leachates from handpacked soil columns was higher in Burgos (100%) than in Toledo (80%), because of the larger adsorption of hexazinone in this last soil. No differences in simazine leaching between both soils were found, although the total amount of pesticide recovered in leachates (40% in the two soils) was lower for simazine than for hexazinone. Finally, lower degradation was found in Burgos (t1/2 = 91 d) vs Toledo (t1/2 = 47 d), directly related with the high OM content of Toledo. No half-life was calculated for simazine in Toledo because no changes in herbicide soil content were observed during the period of time studied. In the case of Burgos, the half-life for simazine was 50 days. The field residues study showed larger persistence of simazine than hexazinone mainly due to the higher adsorption and lower mobility of simazine in the two soils. The lower persistence of hexazinone in Toledo soil than in Burgos soil is related to the larger rainfall occurred in this soil besides the higher degradation of this herbicide observed in Toledo soil. The much lower temperature in Burgos than in Toledo soil during winter contribute to the higher persistence of the two herbicides in Burgos soil.     

Persistent organic pollutants (POP) in a benthic omnivore--a comparison between lake and stream crayfish populations

We investigated the accumulation of PCB and DDT in crayfish populations in 10 streams in southern Sweden. The results were compared with an earlier study on crayfish in lakes from the same area. We found that the concentration of pollutants in crayfish did not differ between the two types of systems. Variation in body burden was higher in stream living crayfish probably because of the higher influence from pollutants deposited in the catchment area and the more dynamic transport in streams. In streams, p,p'-DDE concentrations were positively correlated to trophic status (total phosphorous) while PCB did not show any correlation with the nutrient regime. Further, mean SigmaPCB and p,p'-DDE concentrations in crayfish did not correlate in streams. We suggest that the sources of the two pollutants differ for stream living crayfish. The results indicate that crayfish in streams are affected to a higher degree to pollutants in the catchment area and the precipitation regime. In lakes, internal processes govern uptake of pollutants in crayfish.     

Polychlorinated biphenyls and some pesticides in perch (Perca fluviatilis) from inland waters of Latvia

Polychlorinated biphenyls (PCBs), DDT-related substances, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB) were analysed in perch (Perca fluviatilis) from Latvian lakes and rivers. DDE is present in the highest concentrations in all samples; 62-170 ng/g lipid weight in perch from rural areas and 460 ng/g in perch from the Riga area. Individual dominating PCB congeners were in the range 16-45 ng/g and 200-210 ng/g, respectively. The degree of contamination of rural areas in Latvia of these organohalogen substances is in the same range as in background areas in Sweden. Riga, the major urban area in Latvia, is shown to be more polluted with PCBs than other areas in Latvia.     

Fogwater chemistry in a wood-burning community, western Oregon

Fogwater chemistry in Corvallis, Oregon, a wood-burning community (pop. approximately 43,000) was compared with the chemistry of fogwater collected in more remote and in more highly industrialized areas. The fogwater was not acidic (median pH = 5.7) and was usually dominated by SO4=, NO3-, and NH4+ whose concentrations were generally lower than in fogwater in other urban areas but higher than in remote areas. Concentrations of formic and acetic acids (medians = 61 and 52 microN, respectively) were comparable to those in fogwater in Los Angeles, California and were typically much higher than concentrations in fogwater from more remote areas. Formate and acetate concentrations were often comparable to those of SO4= and NO3-. Formaldehyde concentrations (range = 0.4-3.0 mg L-1) were comparable to those in fogwater in some urban areas of southern California, yet lower than concentrations in highly industrialized areas of southern California. Because concentrations of organic compounds in Corvallis fogwater were often comparable to those in larger urban areas, sources in addition to motor vehicles must be important in Corvallis. Additional sources may be natural and anthropogenic, the latter including residential wood burning and wood products industries.     

Lead Concentrations in Detroit,New York,and Los Angeles Air

Lead concentrations in air were measured at 12 sites in Detroit, New York and Los Angeles as part of a program to relate automobile emissions and polynuclear aromatic hydrocarbons in air. The information on lead is reported separately because of the current interest in lead as an air pollutant. Sampling was conducted by means of a large “absolute” filter and equipment contained in a step-van truck. A portion of the filter was macerated in nitric acid and the lead determined spectrographically. The combined annual average lead concentration for four sites in metropolitan Los Angeles was approximately 40% higher than the combined averages of either the five sites in metropolitan New York or the three sites in metropolitan Detroit. Concentrations ranged from 0.4 ug/M³ at Santa Monica, to 18.4 ug/M³ at a Los Angeles Freeway Interchange. Concentrations were generally highest in freeway areas, intermediate in commercial areas, and lowest in residential areas. They were about 40% higher in daytime than at night. Average lead concentrations were highest during autumn in New York and winter in Los Angeles reflecting an inverse relationship with wind speed. Correlation coefficients between lead and carbon monoxide, at all sites, were statistically non-zero with 99% confidence and varied from 0.75 to 0.96. Lead concentrations in this study were higher than concentrations reported by others for Detroit, New York, and Los Angeles, presumably because sampling in this study was closer to traffic. However, concentrations in this study were lower than in-traffic concentrations given in the literature.