Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Characterisation of cholinesterases and evaluation of the inhibitory potential of chlorpyrifos and dichlorvos to Artemia salina and Artemia parthenogenetica

In this study, the acute toxicity of the organophosphorous pesticides dichlorvos and chlorpyrifos to two different species of Artemia (A. salina and A. parthenogenetica) was evaluated. In addition, the in vivo effect of these two pesticides on cholinesterase (ChE) activity of both A. salina and A. parthenogenetica was also determined. The characterisation of the ChE, using different substrates and specific inhibitors, and the normal range of activity in non-exposed individuals were previously investigated for both species. The results obtained indicate that the ChE of A. salina is different from that of A. parthenogenetica and that both enzymes cannot be classified neither as acetylcholinesterase nor as butyrylcholinesterase since they show intermediary characteristics between the two vertebrate forms. The range of normal ChE activity was 2.65+/-0.15 U/mg protein for A. salina, and 3.69+/-0.17 U/mg protein for A. parthenogenetica. Significant in vivo effects of both pesticides on Artemia ChE activity were found, at concentrations between 5.38 and 9.30 mg/l for dichlorvos and between 1.85 and 3.19 mg/l for chlorpyrifos. Both Artemia species are resistant to these pesticides and they are able to survive with more than 80% ChE inhibition. However, A. parthenogenetica is more resistant than A. salina, with about a 95% reduction in its ChE activity respect to the control for nauplii exposed to the median lethal concentrations (LC50), without lethal effects after 24 h of exposure.     

Toxicity and detoxification of Swedish detergents and softener products

Detergents and softeners are used in large quantities and some of their ingredients are highly toxic to aquatic organisms. In the present study the acute toxicity to Daphnia magna was determined for 26 detergents and five softener Swedish products. Only one of the detergents had a 48-h EC50 > 100 mg/l. The 48-h EC50 for the other 25 detergents ranged from 4 to 85 mg/l. The 48-h EC50 for the five softeners ranged from 15 to 166 mg/l. Detoxification tests, with and without inoculum of sewage organisms, showed that all tested products were detoxified to some extent after 16 days and that the rate of detoxification was considerably higher with addition of sewage organisms. Toxicity to D. magna of the detergents and softeners, and the biotic detoxification rate was correlated with the concentration of surfactants used in formulating the products (more surfactants increased toxicity and a slower rate of detoxification). These results emphasize the importance of biological purification of domestic wastewater containing detergents and a suggested development of less toxic and more easily degradable surfactants.     

Spatial and temporal trend of Chinese manure nutrient pollution and assimilation capacity of cropland and grassland

Dynamics of livestock and poultry manure nutrient was analyzed at a provincial scale from 2002 to 2008. The nutrient capacity of 18 kinds of croplands and grasslands to assimilate nutrients was assessed in the same temporal–spatial scale. Manure nitrogen (N) had increased from 5.111 to 6.228 million tons (MT), while manure phosphorus (P) increased from 1.382 to 1.607 MT. Manure N and P share similar spatial patterns of yields, but proportion of specialized livestock husbandry and contribution of leading livestock categories (swine, cattle, cow, sheep, layer chicken, broiler chicken) were different. The nutrients generated from dominant seven provinces took more than about half of total manure N in China. After subtracting the chemical fertilizers, there were some manure nutrient capacities in western part of China. Risk analysis of manure nutrient pollution overload in eastern and southern parts of China was serious, which should restrict livestock's developments. Amount of chemical fertilizers applied should be reduced to make room for manure nutrients. For the sake of greenhouse effects, the emission of methane (CH₄) and nitrous oxide (NO _x ) emissions in China is serious for the global change, thus merits further statistics and studies. The spatial and temporal pattern of Chinese manure nutrient pollution from livestock and the assimilation capacity of cropland and grassland can provide useful information for policy development on Chinese soil environment and livestock.     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death,age, and season

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 microg/m3 particulate matter (PM) of median diameter < or = 10 microm (PM10); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO2; 1.6% (1.1-2.0%) per 31.2 ppb O3; and 0.9% (0.7-1.2%) per 9.4 ppb SO2 (daily maximum concentration for O3, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM10 and SO2. Larger effect sizes were observed for respiratory mortality for all pollutants except O3. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Combined effects of soil moisture and carbaryl to earthworms and plants: simulation of flood and drought scenarios

Studying tolerance limits in organisms exposed to climatic variations is key to understanding effects on behaviour and physiology. The presence of pollutants may influence these tolerance limits, by altering the toxicity or bioavailability of the chemical. In this work, the plant species Brassica rapa and Triticum aestivum and the earthworm Eisenia andrei were exposed to different levels of soil moisture and carbaryl, as natural and chemical stressors, respectively. Both stress factors were tested individually, as well as in combination. Acute and chronic tests were performed and results were discussed in order to evaluate the responses of organisms to the combination of stressors. When possible, data was fitted to widely employed models for describing chemical mixture responses. Synergistic interactions were observed in earthworms exposed to carbaryl and drought conditions, while antagonistic interactions were more representative for plants, especially in relation to biomass loss under flood-simulation conditions.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediately after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediately after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Abstract

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediatly after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediatly after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.     

Kinetic and structural relationships of transition monomeric and oligomeric carboxyl- and choline-esterases

The kinetic and structural relationships of eight electrophoretically pure mammalian serum and liver serine carboxylesterases (CE) and cholinesterases (ChE) have been studied. Eight CE's and ChE's, which were fully resolved but only partially purified, provided additional information. Five of the electrophoretically pure esterases were monomeric, and of these, four belonged to a new and widely distributed class. These four monomeric esterases hydrolyzed choline esters, but at widely differing rates. Thus two were termed monomeric butyrylcholinesterases, mBuChE I and II, and two were monomeric CE's (mCE). The rabbit liver mCE was not a subunit of the oligomeric CE (oCE), although the oCE also hydrolyzed choline esters at a very low rate. The complex kinetics of the mCE's, mBuChE's, oCE's, and of the oligomeric BuChE's of horse and human serum could be interpreted according to a single reaction scheme involving an allosteric site and the equation derived from it. Thus activation and inhibition at high substrate concentrations, together with sigmoidal activity versus substrate concentration plots, all of which characterize the reactions of these esterases, could be interpreted by a single scheme and equation. Structural and kinetic comparisons showed a progressive transition of properties from the oCE's through the mCE's to the oBuChE's. One of the purified mCE's was from horse serum, and it exhibited physical and kinetic properties unlike those of the liver mCE's or oCE's.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Meta-Analysis of Time-Series Studies of Air Pollution and Mortality: Effects of Gases and Particles and the Influence of Cause of Death,Age, and Season

Abstract

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 μg/m³ particulate matter (PM) of median diameter <10 μm (PM₁₀); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO₂; 1.6% (1.1-2.0%) per 31.2 ppb O₃; and 0.9% (0.7-1.2%) per 9.4 ppb SO₂ (daily maximum concentration for O₃, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM₁₀ and SO₂. Larger effect sizes were observed for respiratory mortality for all pollutants except O₃. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Mathematical description, optimization and prediction of synergistic interaction of fluoride and xylitol

The potential ability of various physical or chemical agents to enhance their effect when they are applied simultaneously with each other is well-known. The purpose of this study was to adjust a simple mathematical model to describe, optimize and predict a synergistic interaction between fluoride and xylitol on acid production by mutans streptococci. The model suggests that the synergism is caused by the additional effective damage arising from an interaction of sublesions induced by each agent. These sublesions are considered to be ineffective when each agent is used individually. The predictions of the model were verified by comparison with experimental data published by other researchers. It was shown that the model describes the experimental data, predicts the greatest value of the synergistic effect and the condition under which it can be achieved. The synergistic effect appeared to decline with any deviation from the optimal value of the ratio of effective damages produced by each agent alone.     

Enrichment and isolation of endosulfan degrading and detoxifying bacteria

In the present study, degradation of endosulfan by a mixed culture isolated from a pesticide-contaminated soil was studied in batch experiments. After two weeks of incubation, the mixed culture was able to degrade 73% and 81% of alpha and beta endosulfan respectively. Endodiol was identified by GC/MS as degradation intermediate. The toxicity studies of endosulfan before and after degradation were carried out using micronucleus assay on human polymorphonuclear cells. The findings suggested that the metabolism of endosulfan isomers by the mixed culture was accompanied by significant reduction in the toxicity. Studies were also carried out to quantify the degradation potential of the individual species in the mixed bacterial culture. Two cultures identified by 16S rRNA as Stenotrophomonas maltophilia and Rhodococcus erythropolis were found to be responsible for majority of the degradation by the mixed culture. S. maltophilia showed better degradation efficiency compared to that by R. erythropolis. This is the first report of endosulfan degradation using the above-mentioned organisms.     

Effects of surfactant and temperature on biotransformation kinetics of anthracene and pyrene

The biotransformation and mineralization of a mixture of two polycyclic aromatic hydrocarbons (PAHs), anthracene and pyrene, which are known contaminants of soil and groundwater, by an enrichment culture in the presence or absence of 100 mg l(-1) Tergitol NP-10, a non-ionic surfactant, and at temperatures of 10 degrees C and 25 degrees C were investigated. The overall biotransformation of 2 mg l(-1) total PAHs with free cell suspensions in batch culture was greater than 97.2% at both examined temperatures. At 25 degrees C, the overall mineralization of anthracene was 48.8% and that of pyrene was 66.1%. However, the decrease of temperature to 10 degrees C had a negative effect on the mineralization of PAHs and reduced it to 18.5% and 61.5% for anthracene and pyrene, respectively. Using a higher PAHs concentration of 20 mg l(-1) at 25 degrees C, the overall biotransformation of anthracene was 80.7% and that of pyrene was 100%, where only 17.3% anthracene and 7.6% pyrene were mineralized to carbon dioxide and water. The addition of surfactant at 25 degrees C increased the overall mineralization of anthracene and pyrene to 33.0% and 27.6%, respectively. However, the addition of surfactant at 10 degrees C had a negative impact on the overall biotransformation of anthracene and pyrene, reducing them to 20.6% and 14.0%, respectively. These results have significant implications in the bioremediation of PAHs-contaminated sites.