Pesticide fate in tropical wetlands of Brazil: an aquatic microcosm study under semi-field conditions

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT(50) by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT(50) > or = 47 d); in large water/sediment systems endosulfan beta, atrazine, metolachlor, and simazine showed the slowest dissipation (DT(50) > or = 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11-35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.     

Dissolution of resin acids, retene and wood sterols from contaminated lake sediments

The dissolution potency of hydrophobic resin acids (RAs), retene and wood sterols from sediments was studied. These wood extractives and their metabolites are sorbed from pulp and paper mill effluents to downstream sediments. With harmful components like these, sediments can pose a hazard to the aquatic environment. Therefore, sediment elutriates with water were produced under variable conditions (agitation rate and efficiency, time), and concentrations of the dissoluted compounds were analyzed. Both naturally contaminated field sediments and artificially spiked sediments were studied. By vigorous agitation RAs can be released fast from the sediment matrix and equilibrium reached within 3 days. Compared to RAs, desorption of retene from lake sediment was slower and did not completely reach equilibrium in 23 days. Sterols spiked to pristine sediment with a 33-day contact time desorbed faster than those associated authentically with industrial sediment of from a contaminated lake. Simulating the water turbulence adjacent to a sediment surface by low and high rate of agitation in the laboratory, an increase in the mixing rate after 43-day elutriation suddenly released a high amount of wood sterols. The results indicate wide variation between hazardous chemicals in their tendency to dissolution from sediment solids. Erosion and hydrology adjacent to the sediment surface, as well as risks from dredging activities of sediments, may expose lake biota to bioactive chemicals.     

Distribution characteristics of nonylphenols in the artificial Lake Shihwa, and surrounding creeks in Korea

Nonylphenols were determined from the water, suspended particle, and sediment samples taken from the Lake Shihwa in Korea and its surrounding creeks flowing through municipal and industrial areas, and into the lake. The nonylphenols were detected at the concentration ranges of 0.0-41.3 microg/l, 0.0-116.6 and 0.3-31.7 mg/kg in water, suspended particle and sediment samples respectively. The contamination levels of nonylphenols were increased along the down stream. Considerably high levels of nonylphenols were found at the industrial area compared to the municipal area. No remarkable differences were found between the isomer patterns of nonylphenols for the sample matrices of each sampling site, i.e. water, suspended solids and sediment. Strong correlations between water and sediment with 10(5.2) of the mean partition coefficient (Koc ) were observed. These indicate that most of nonylphenols came from industrial wastewater at high level. It is thought that the water quality of the Lake Shihwa is affected greatly by industrial environments surrounding.     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Environmental impact of two successive chemical treatments in a small shallow eutrophied lake: Part I. Case of aluminium sulphate

This paper deals with the efficiency and effects of addition of aluminium sulphate on soft water quality of a shallow eutrophic lake. Almost all the controlled variables improved with treatment, especially nutrient concentrations such as soluble reactive phosphorus (SRP) and transparency. However, aluminium sulphate was not added in sufficient quantity to reduce the total phosphorus content. SRP concentration was significantly reduced in the short term. Moreover, external loading of phosphorus was high and not taken into account by the in-lake treatments. Finally, resuspension of sediment (polymictic lake) removed the alum hydroxide layer on the sediment surface, which reduced treatment effectiveness. No significant pH decrease was noted following alum addition. According to bibliographical toxicological data, monomeric aluminium content does not show any toxic effect on aquatic fauna and flora. In spite of low SRP in the water column, the treatment did not prevent appearance of Microcystis sp. colony (> 10 colony per ml) approximately 30 days after alum application.     

Tetrabromobisphenol A: tissue distribution in fish, and seasonal variation in water and sediment of Lake Chaohu, China

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardants (BFRs). It has been detected in various environment media and has been approved to be high toxic to aquatic organisms. However, the exposure levels of TBBPA in the main watersheds in China have not been investigated sufficiently. In this study TBBPA concentrations in water, sediment and tissues of four fish species from Lake Chaohu were determined. Spatial and temporal distribution patterns of TBBPA in water and sediment, and the relationship among TBBPA concentrations in fish tissues and fish size were analyzed. The results showed that the maximum TBBPA concentration in sediment was 518 ng/g in March 2008. It is almost the highest value than those ever reported anywhere in the world. In lake water, TBBPA level reached the maximum value of 4.87???g/L in July. Tissue distributions of TBBPA in four fish species were similar, and the mean concentrations in the fish were in the range of 28.5?C39.4 ng/g, much higher than those reported in Japan, Europe, and the United States. The maximum concentrations of TBBPA were found in kidneys where TBBPA concentration was positively correlated with fish size of Cyprinus carpio. Results demonstrated a widespread distribution of TBBPA in Lake Chaohu. The source was mainly inflow rivers near the cities. The distribution coefficient among water, fish, and sediment was 1:28:117. This indicated that sediment was the main repository for TBBPA within Lake Chaohu. Furthermore, TBBPA may pose a potential ecological risk in the lake during summer.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.     

Arsenic and mercury concentrations in major landscape components of an intensively cultivated watershed

To provide an understanding of arsenic (As) and mercury (Hg) concentrations in soil, sediment, water, and fish tissues, samples were collected from a Mississippi River alluvial floodplain located in northwest Mississippi. As concentrations increased approximately an order of magnitude from water (5.12 micrograms/l) to fish tissues (36.99 micrograms/kg) and an additional two orders of magnitude in soils, lake sediments, and wetland sediments (5728, 5614, and 6746 micrograms/kg), respectively. Average Hg concentrations in water, soils, lake sediments, and fish were 2.16 micrograms/l, 55.1, 14.5 and 125 micrograms/kg, respectively. As and Hg concentrations were within published ranges for uncontaminated soil, water, and sediments. As concentrations represented a low risk. Hg concentrations were also low but showed a greater tendency to concentrate in fish tissue. The dominant mode of entry of these materials into aquatic systems is through storm-generated runoff. Since both metals accompany sediments, agricultural conservation practices such as reduced tillage, buffer riparian strips, and bordering sediment ponds or drainage wetlands will minimize watershed input to aquatic systems.     

Bottom sediment as a source of organic contaminants in Lake Mead, Nevada, USA

Treated wastewater effluent from Las Vegas, Nevada and surrounding communities’ flow through Las Vegas Wash (LVW) into the Lake Mead National Recreational Area at Las Vegas Bay (LVB). Lake sediment is a likely sink for many hydrophobic synthetic organic compounds (SOCs); however, partitioning between the sediment and the overlying water could result in the sediment acting as a secondary contaminant source. Locating the chemical plumes may be important to understanding possible chemical stressors to aquatic organisms. Passive sampling devices (SPMDs and POCIS) were suspended in LVB at depths of 3.0, 4.7, and 6.7 (lake bottom) meters in June of 2008 to determine the vertical distribution of SOCs in the water column. A custom sediment probe was used to also bury the samplers in the sediment at depths of 0-10, 10-20, and 20-30 cm. The greatest number of detections in samplers buried in the sediment was at the 0-10 cm depth. Concentrations of many hydrophobic SOCs were twice as high at the sediment-water interface than in the mid and upper water column. Many SOCs related to wastewater effluents, including fragrances, insect repellants, sun block agents, and phosphate flame retardants, were found at highest concentrations in the middle and upper water column. There was evidence to suggest that the water infiltrated into the sediment had a different chemical composition than the rest of the water column and could be a potential risk exposure to bottom-dwelling aquatic organisms.     

The fate of endosulfan in aquatic ecosystems

Endosulfan, one of the major pesticides used in cotton-growing, is of environmental concern because of its toxicity to fish and its apparent persistence in the environment. This study examines the distribution and degradation pathways for endosulfan in an aquatic system and the processes by which it is removed. In the alkaline waters of the cotton region, hydrolysis is the dominant degradation process. By this mechanism alone, the expected half-lives for the alpha- and beta-endosulfan isomers were found to be 3.6 days and 1.7 days, respectively. Partitioning studies showed, however, that the major proportion of endosulfan would associate with the sediments (log Koc(alpha) 3.6 and log Koc(beta) 4.3). Field studies confirmed the presence of high concentrations in sediments. Microcosm experiments showed that loss of endosulfan was slower than predicted from hydrolysis rates. Models are presented to explain how desorption from sediment limits the loss of endosulfan from a system.     

Microbial metabolism of N-Phenyl-1-naphthylamine in soil, soil suspensions, and aquatic ecosystems

N-Phenyl-1-naphthylamine (PNA) was degraded and mineralized in nonsterile aquatic and terrestrial samples. Degradation in unsupplemented sewage and lake water was detected in 3 to 6 days with half-lives of 5 and 10 days, respectively. In sewage and lake water supplemented with a readily degradable carbon source, degradation began in 1 and 5 days with half-lives of 2 and 8 days, respectively. Sewage samples converted between 20 and 30% of labeled [¹⁴C]-PNA to ¹⁴CO₂ in 35 days while lake water samples reached 10% conversion to ¹⁴CO₂ in 12 days. Soil samples and soil suspensions converted from 15 to 35% of [¹⁴C]-PnA to ¹⁴CO₂ in 11 days. PNA was microbiologically converted in lake water to two products that were tentatively identified by gas-liquid chromatography and mass spectroscopy as dihydroxy and N-acetyl derivatives.     

Arsenic mobility in contaminated lake sediments

An arsenic contaminated lake sediment near a landfill in Maine was used to characterize the geochemistry of arsenic and assess the influence of environmental conditions on its mobility. A kinetic model was developed to simulate the leaching ability of arsenic in lake sediments under different environmental conditions. The HM1D chemical transport model was used to model the column experiments and determine the rates of arsenic mobility from the sediment. Laboratory studies provided the information to construct a conceptual model to demonstrate the mobility of arsenic in the lake sediment. The leaching ability of arsenic in lake sediments greatly depends on the flow conditions of ground water and the geochemistry of the sediments. Large amounts of arsenic were tightly bound to the sediments. The amount of arsenic leaching out of the sediment to the water column was substantially decreased due to iron/arsenic co-precipitation at the water-sediment interface. Overall, it was found that arsenic greatly accumulated at the ground water/lake interface and it formed insoluble precipitates.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in a sediment–water system

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (¹⁴C-CfP) was studied for 28 days in lab assays using a sediment–water system derived from a German location. Mineralization was 5.21% of applied ¹⁴C after 28 days exhibiting a distinct lag phase until day 14 of incubation. Portions of radioactivity remaining in water phases decreased at moderate rate to 18.48% after 28 days; 62.46% were still detected in water after 14 days. Soxhlet extraction of the sediment using acetonitrile released 35.56% of applied ¹⁴C with day 28, while 33.99% remained as non-extractable residues. A remarkable increase of bound ¹⁴C was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with microbial activity of the sediment as determined by dimethyl sulfoxide reduction. Dissolved oxygen and pH value of water phases remained almost constant for 28 days. Analyses of Soxhlet extracts of the sediment and ethyl acetate extracts of water phases by radio-TLC and radio-HPLC revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed. DT₅₀ values (based on radio-HPLC) were below 1 day (CfP) and slightly above 28 days (Cf). Further metabolites were not detected. Fractionation of humic and non-humic components of the sediment demonstrated that CfP's non-extractable residues were predominantly associated with fulvic acids up to 14 days of incubation (3.36%), whereas after 28 days, the majority of radioactivity was found in the humin/mineral fraction (13.30% of applied ¹⁴C). Due to high-performance size-exclusion chromatography of the fulvic acids fraction derived from assays incubated for 28 days, this portion of ¹⁴C was firmly, possibly covalently bound to fulvic acids and did not consist of CfP or Cf. Using an isolation strategy comprising preincubation of sediment with CfP and mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the sediment examined. It grew on ¹⁴C-CfP as sole carbon source with evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and 16S rDNA sequence analysis. Its sequence exhibited high similarity with that of Nocardioides aromaticivorans strain H-1 (98.85%; DSM 15131, JCM 11674).     

Contribution of winter to the annual CH4 emission from a eutrophied boreal lake

The springtime methane (CH4) emission from a small, eutrophied boreal lake was assessed during the winter ice-cover by measurement of gas ebullition and CH4 accumulation in the water column in association with the development of oxygen depletion after ice formation. The winter CH4 production was estimated to result in a loss of 3.6-7.9 g CH4 m(-2) from the lake to the atmosphere during the short period of ice melt. This could account for 22-48% of the annual CH4 emission from the pelagic zone of the lake. The contribution of winter to the annual CH4 release can be similar or even higher in seasonally ice-covered northern aquatic ecosystems than in northern terrestrial wetlands, thus winter must be considered in any studies into the aquatic CH4 emissions. The trophic state and wintertime oxygen conditions, linked to the changes in land-use in the catchments and climate, are important factors controlling the springtime lake CH4 emissions.     

潜水丁坝在湖滨带生态恢复中的应用

为保护和稳固湖滨带,在太湖梅梁湾进行生态恢复研究,并成功地实施了示范工程.沿湖滨带共构筑14道潜水丁坝,每道长23～28 m,坝间距为40～80 m,坝上种植芦苇和菰.构筑的潜水丁坝能经受住太湖常见大风袭击和湖流淘蚀,芦苇和菰等长势良好,湖滨原有芦苇带在一定水深范围内每年向湖延伸2～5 cm,坝上其他水生植物和底栖动物螺蛳等自然繁衍.潜水丁坝所起作用为利用自然力改变岸边流场,使泥沙在湖滨带预定沉积区内沉积,减缓岸边侵蚀和降低沉积物再悬浮,从而为湖滨带水生植物生长创造良好的生境条件.研究发现,在微风条件下,潜水丁坝群能有效拦截麇集于岸边的蓝绿藻,并在湖滨带进行消化降解.研究提出的构筑潜水丁坝并种植水生植物的方案为湖滨带生态恢复提供了一种新的探索途径.     

Passive sampling of selected endocrine disrupting compounds using polar organic chemical integrative samplers

Two types of polar organic chemical integrative samplers (pharmaceutical POCIS and pesticide POCIS) were examined for their sampling efficiency of selected endocrine disrupting compounds (EDCs). Laboratory-based calibration of POCISs was conducted by exposing them at high and low concentrations of 14 EDCs (4-alkyl-phenols, their ethoxylate oligomers, bisphenol A, selected estrogens and synthetic steroids) for different time periods. The kinetic studies showed an integrative uptake up to 28 days. The sampling rates for the individual compounds were obtained. The use of POCISs could result in an integrative approach to the quality status of the aquatic systems especially in the case of high variation of water concentrations of EDCs. The sampling efficiency of POCISs under various field conditions was assessed after their deployment in different aquatic environments.     

Dissipation of glyphosate and aminomethylphosphonic acid in water and sediment of two Canadian prairie wetlands

Glyphosate [N-(phosphonomethyl)glycine] is the active ingredient of several herbicide products first registered for use in 1974 under the tradename Roundup. The use of glyphosate-based herbicides has increased dramatically over the last two decades particularly in association with the adoption of glyphosate-tolerant crops. Glyphosate has been detected in a range of surface waters but this is the first study to monitor its fate in prairie wetlands situated in agricultural fields. An ephemeral wetland (E) and a semi-permanent wetland (SP) were each divided into halves using a polyvinyl curtain. One half of each wetland was fortified with glyphosate with the added mass simulating an accidental direct overspray. Glyphosate dissipated rapidly in the water column of the two prairie wetlands studied (DT(50) values of 1.3 and 4.8 d) which may effectively reduce the impact of exposure of aquatic biota to the herbicide. Degradation of glyphosate to its major metabolite aminomethylphosphonic acid (AMPA) and sorption of the herbicide to bottom sediment were more important pathways for the dissipation of glyphosate from the water column than movement of the herbicide with infiltrating water. Presently, we are not aware of any Canadian guidelines for glyphosate residues in sediment of aquatic ecosystems. Since a substantial portion of glyphosate entering prairie wetlands will become associated with bottom sediments, particularly in ephemeral wetlands, guidelines would need to be developed to assess the protection of organisms that spend all or part of their lifecycle in sediment.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Distribution of total mercury and methylmercury in lake sediments in Arctic Ny-Ålesund

The toxicities and bioavailabilities of total mercury (THg) and methylmercury (MeHg) in aquatic systems have made them the subjects of recent research. In this study, we collected a lake sediment core from Ny-Ålesund in Svalbard and analyzed the distributions of THg and MeHg in the sediments. The increased trend of THg was caused by anthropogenic contamination since the 14th century through long-range transportation, especially after the industrial era. However, the peak values of Hg in surface sediment samples could be explained by the increased algal scavenging process in recent decades. All the biogeochemical proxies (e.g., pigments and diatom biomass) revealed recent sharp increases in aquatic primary production due to the current climate warming. Rock-Eval analyses indicated that algal-derived organic matter took up a large portion, and quantitative calculation showed that 89.6-95.8% of the Hg in post-1950 could be explained by scavenging. The distribution of MeHg has a close relationship with total Hg and organic matter. The oxidation-reduction condition is one of the possible factors affecting the methylation rates in H2 lake sediments. Higher algal productivity and organic matter actually led to the increased trend of methylation in the uppermost sediment. This study supports some new key hypotheses on climate-driven factors affecting Hg and MeHg cycling in High Arctic lake sediments.     

Total,dissolved, and bioavailable metals at Lake Texoma marinas

Dissolved metals in water and total metals in sediments were measured at marina areas in Lake Texoma during June 1999 to October 2001, and October 2001, respectively. The metals most often found in the highest concentrations in marina water were Na and Ca, followed by Mg and K. Elevated Cu levels detected in lake water appeared to be associated with Cu based anti-fouling paint used on boats. Metal concentrations in sediment were much higher than in water. The relative order of the concentration in sediment was Ca > Al > Fe > K > Mg > Na. Elevated Cu level at specific locations appeared to be associated with local anthropogenic sources of boat repair activities. There were positive relationships between several metal elements in water and sediment. Metals in 16 sediments from lake marinas were extracted with a weak electrolyte solution [0.1 M Ca(NO3)2] to predict the bioavailability of metals. Among the five heavy metals studied (As, Cd, Cr, Cu and Zn), Cu was the most bioavailable in Lake Texoma marinas.