Chlorpyrifos acute exposure induces hyperglycemia and hyperlipidemia in rats

In this study we evaluated the hyperglycemic and hyperlipidemic effects of chlorpyrifos (CPF) after an acute exposure in rats. The mechanisms involved in hyperglycemia induced by CPF were studied. A single dose of CPF (50 mg kg⁻¹, subcutaneous, s.c.) was administered to overnight-fasted rats. Glucose and corticosterone levels, lipid status and paraoxonase (PON1) activity were determined in plasma of rats. Cardiovascular risk factors and the atherogenic index were calculated. Glycogen levels, tyrosine aminotransferase (TAT) and glucose-6-phosphatase (G6Pase) activities were determined in livers of rats. Cerebral acetylcholinesterase (AChE) activity was also determined. CPF caused an increase in glucose and glycogen levels as well as in TAT and G6Pase activities. The CPF exposure caused an increase in corticosterone levels, an inhibition of AChE activity and a reduction of PON1 activity. Regarding the lipid status, CPF induced an increase in triglycerides (TG) and low-density lipoprotein-cholesterol (LDL) levels and a decrease in high-density lipoprotein (HDL) levels associated with an increase of cardiovascular risk factors and the atherogenic index. The present study demonstrated that a single CPF administration caused hyperglycemia and hyperlipidemia in rats. The activation of the gluconeogenesis pathway, probably elicited by hypercorticosteronemia, is involved in the hyperglycemic effect of CPF in rats.     

Immobilised microbial reactor for the biotransformation of hexavalent chromium

Out of an array of bacterial strains isolated from soil contaminated with effluents from electroplating wastewater, Bacillus coagulans exhibited the maximum Cr(VI) reduction potential. The feasibility of an immobilized B. coagulans bioreactor for hexavalent chromium reduction was investigated. Experimental results demonstrated that near complete removal of Cr(VI) was achieved in the reactor with an initial Cr(VI) concentration of 26 mg/l and reactor time of 24 h. The removal efficiency in the bioreactor was significantly affected by the influent Cr(VI) concentration, the Cr(VI) loading rate, the reaction time and the amount of Cr(VI) reduced by the biomass.     

Retention of Cd, Zn and Co on hydroxyapatite filters

This study qualifies and quantifies the immobilization of Cd, Zn and Co, (used as models of bivalent metal ions due to their relevant toxicity) in filters of synthetic hydroxyapatite (HAP) [Ca5(PO4)3OH]. They were flushed with solutions containing Cd (1 x 10(-5)M), Zn and Co (1 x 10(-4)M) at constant pH (8.6) and ionic strength (0.01 M). The concentration of these metal ions in the outlet was measured by ICP-OEM spectroscopy. The software PHREEQC (version 2.4.2) was used to model sorption process and the potential effect of salinity (KCl), pH, alkalinity (NaHCO3) and hardness (CaCl2) over the efficiency of the treatment. Results showed an excellent retention capacity of HAP for Cd, Zn and Co. Sorption data were successfully described considering a mix model of surface complexation onto phosphate surface groups, ionic exchange in surface calcium sites and the precipitation of ZnO. Co exchange and surface complexation constants (Kex and Kc) were taken from previous experiments, while KexCd=0.32 and KcCd=0.63 were estimated from our modeling results. Predictive values of metal ion sorption show that: (a) an increase in hardness does not play a significant role in the retention capacity of these metals on HAP; (b) an increase in alkalinity promotes the precipitation of MeCO3 which could alter the hydrodynamic of the column; (c) a decrease in pH and an increase in salinity inhibit ZnO precipitation enhancing Zn and Cd adsorption and decreasing Co retention on HAP.     

Nonpoint source pollution of urban stormwater runoff: a methodology for source analysis

The characterization and control of runoff pollution from nonpoint sources in urban areas are a major issue for the protection of aquatic environments. We propose a methodology to quantify the sources of pollutants in an urban catchment and to analyze the associated uncertainties. After describing the methodology, we illustrate it through an application to the sources of Cu, Pb, Zn, and polycyclic aromatic hydrocarbons (PAH) from a residential catchment (228 ha) in the Paris region. In this application, we suggest several procedures that can be applied for the analysis of other pollutants in different catchments, including an estimation of the total extent of roof accessories (gutters and downspouts, watertight joints and valleys) in a catchment. These accessories result as the major source of Pb and as an important source of Zn in the example catchment, while activity-related sources (traffic, heating) are dominant for Cu (brake pad wear) and PAH (tire wear, atmospheric deposition).     

Synthesis, isolation and purification of C10-C13 polychloro-n-alkanes for use as standards in environmental analysis

Short chain (C10-C13) polychloro-n-alkanes (sPCAs) mixtures were synthesized by refluxing pure n-alkane (> 99%) with sulfuryl chloride (SO2Cl2) in the presence of UV-light (550 W). The free radical initiated reactions produced analogs containing approximately 4-9 chlorine atoms on each carbon chain. Purification of reaction products was achieved by adsorption chromatography on Florisil. The products were characterized by high-resolution gas chromatography/mass spectrometry (HRGC/MS) operated in the electron capture negative ionization (ECNI) and in electron ionization (EI) modes. Individual standards can now be combined to create standards whose profiles resemble that of environmental samples. Quantification of a known amount of the newly synthesized sPCAs mixture, using an industrial formulation as an external standard, resulted in an overestimation (approximately 28%) in its true value.     

A new method to assess mercury emissions: a study of three coal-fired electric-generating power station configurations

U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of approximately 5 min per sample, this instrumental methodology can directly analyze total Hg--with no discrete sample preparation--in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.     

The Akoya pearl oyster shell as an archival monitor of lead exposure

The Akoya pearl oyster (Pinctada imbricata) was experimentally exposed to (a) constant levels of lead (Pb) at 180 microg L(-1) for nine weeks, or (b) two short term (pulse) exposures of Pb at 180 microg L(-1) (three weeks each) with an intervening depuration period (three weeks), to assess its utility as an (i) accumulative monitor of Pb contamination and an (ii) archival monitor for discriminating constant versus pulsed Pb exposure events. P. imbricata showed similar reductions in growth (based on shell morphology and wet weight) and Pb accumulation patterns for whole tissue and shell in response to both Pb exposure regimes. Thus the whole oyster was deemed an inappropriate accumulative monitor for assessing short-term temporal variation of Pb exposure and effect. However, using secondary ion mass spectrometry, Pb was shown to accumulate in the successively deposited nacreous layers of the shell of P. imbricata, documenting the exposure history of constant versus pulsed Pb events. Patterns of Pb deposition not only reflected the frequency of Pb exposure events but also their relative durations. Thus, the shell of P. imbricata may be employed as a suitable biological archive of Pb exposure.     

A New Method to Assess Mercury Emissions: A Study of Three Coal-Fired Electric-Generating Power Station Configurations

Abstract

U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of ～5 min per sample, this instrumental methodology can directly analyze total Hg—with no discrete sample preparation—in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.     

Inhalation transfer factors for air pollution health risk assessment

To facilitate routine health risk assessments, we develop the concept of an inhalation transfer factor (ITF). The ITF is defined as the pollutant mass inhaled by an exposed individual per unit pollutant mass emitted from an air pollution source. A cumulative population inhalation transfer factor (PITF) is also defined to describe the total fraction of an emitted pollutant inhaled by all members of the exposed population. In this paper, ITFs and PITFs are calculated for outdoor releases from area, point, and line sources, indoor releases in single zone and multizone indoor environments, and releases within motor vehicles. Typical PITFs for an urban area from emissions outdoors are approximately 10(-6)-10(-3). PITFs associated with emissions in buildings or in moving vehicles are typically much higher, approximately 10(-3)-10(-1).     

Adsorption and characterization of MCPA on DDTMA- and raw-montmorillonite: Surface sites involved

The 4-chloro-2-methylphenoxy acid (MCPA) is an herbicide widely used in agriculture, which generates a great concern about contamination of surface water and serious consequences for human health and the environment. In this work, the adsorption of MCPA on an Argentine montmorillonite (MMT) and its organo-montmorillonite product (OMMT) with different dodecyl trimethyl ammonium loading was investigated. MCPA adsorption on OMMT increases at least 3 times, with respect to the amount determined for MMT. X-ray diffraction and zeta potential analyses indicated the inner (interlayer) and outer surface participate as adsorption sites. Changes in surface electric charge and also interlayer expansion suggest that dimethyl amine (MCPA counterion) was also surface-adsorbed. The larger aggregates of OMMT, without and with MCPA, obtained compared to those of MMT samples, generate an improvement in the coagulation efficiency. This property, particularly after MCPA retention, allows an easier separation of the solids from the solution and enables a simple technological process application.     

Treatment of coke-plant wastewater by biofilm systems for removal of organic compounds and nitrogen

Coke-plant wastewater was treated by an anaerobic-anoxic-aerobic (A(1)-A(2)-O) biofilm system and an anoxic-aerobic (A/O) biofilm system, respectively. At same or similar levels of hydraulic retention time (HRT), the two systems had almost identical chemical oxygen demand (COD) and NH(3) removals, but a different organic-N removal. Set-up of an acidogenic stage benefited for the removal of organic-N and the A(1)-A(2)-O system was more useful for total nitrogen removal than the A-O system. HRT did not have a substantial effect on the COD and NH(3)-N removal efficiencies, but considerably influenced the organic-N removal and distribution of oxidized nitrogen in the final effluent. The GC/MS analysis demonstrated that some refractory compounds were decomposed at the acidogenic stage and resulted in the production of some intermediates, which were more readily degraded in the subsequent aerobic stage. Hence, the A(1)-A(2)-O system had better effluent quality than the A-O system in terms of effluent composition.     

PCDD/PCDF congener profiles in soil and herbage samples collected in the vicinity of a municipal waste incinerator before and after pronounced reductions of PCDD/PCDF emissions from the facility

Congener profiles are the fractional distribution of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) congeners in an environmental release, or in an environmental or biological sample. In 1999, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an old municipal solid waste incinerator (MSWI) from Montcada (Barcelona, Spain). The main goal of the present study was to determine if the environmental PCDD/F levels in the area under direct influence of the facility were mainly due to PCDD/F emissions from the plant. For this purpose, soil and herbage samples were collected near the MSWI before (1998) and after (2000) the technical improvements were performed. PCDD/F congener profiles were determined and compared with those from samples collected in a suburban area of Constantí (Tarragona, Spain) outside of direct emissions from any MSWI. The results of the present study suggest that the MSWI here assessed is not the main responsible for the environmental PCDD/F concentrations in the area under evaluation. Other PCDD/F emission sources in the same area seem also to have a notable impact on the atmospheric levels of these pollutants.     

Congener-distribution patterns and risk assessment of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in Korean human milk

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry in human milk samples from an urban and an industrial area in Korea. All PCB congeners were analyzed to characterize the congener distribution as well as to evaluate the toxic equivalent quotient (TEQ) values and the total concentration. In homologue distributions of PCBs, two distinct patterns were found. The mean concentrations of PCDD/Fs and PCBs were 15.13 and 5.64 TEQ pg/g fat (based on WHO TEF, 1997), respectively. The contamination in Korean human milk is comparable to that found in other countries. From these results a daily intake of 60 TEQ pg/kg/day for an infant was estimated. The assumptions were that the infant breast feeds for 1 year, has an average body weight of 10 kg during this period, and ingests 800 g/day of human milk containing a mean concentration of 20.84 TEQ (PCDD/Fs) pg/g fat (based on primipara mothers).     

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI)

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.     

Adsorption-desorption behaviour of zinc(II) at iron(III) hydroxide-aqueous solution interface as influenced by pH and temperature

Batch studies were carried out to investigate the adsorption of zinc(II) from fresh waters on an iron(III) hydroxide surface maintained at the pH of zero point of charge of hydroxide (ZPC, 6.85) and also on both the acidic (5.5) and alkaline (8.2) sides of pH of ZPC, at 15 and 35 degrees C. Zinc(II) adsorption on iron(III) hydroxide increased with an increase in pH. The rise in temperature from 15 to 35 degrees C increased zinc(II) adsorption at pH 5.5 and 6.85, but decreased it at alkaline pH (8.2). In none of the cases did adsorption attain a maximum adsorption density. The results indicate the presence of heterogeneous sites of varying affinity on the adsorbent. Zinc(II) adsorption followed Langmuir behaviour only at small adsorption densities (less than 10(-2.95) M Zn/kg at pH 5.5) and at higher adsorption densities, the availability of strongest binding sites decreased. Nonspecifically adsorbed zinc(II) (reversible to Ba(II)) decreased with the increase in pH and temperature. Sequential desorption experiments also revealed that desorption of adsorbed zinc(II) decreased with an increase in pH.     

Arsenic(V) removal with a Ce(IV)-doped iron oxide adsorbent

The removal of arsenic(V) by a new Ce-Fe adsorbent was evaluated under various conditions. Under an initial As(V) of 1.0 mg l(-1), the adsorption capacity of the Ce-Fe absorbent was constant around a value of 16 mgg(-1) over a wide pH range (3-7), while a maximum adsorption capacity of 8.3 mgg(-1) was obtained over a narrow pH range around 5.5 for activated alumina, a conventional adsorbent. Kinetics of adsorption obeys a pseudo-first-order rate equation with the rate constant K(ad) as 1.84 x 10(-3) min(-1). The pattern of adsorption of As(V) by the adsorbent fitted well both the Langmuir and Freundlich models. A Langmuir Q(0) of 70.4 mgg(-1) was obtained at an initial pH of 5.0 and temperature of 20 degrees C, significantly higher than those of other adsorbents reported. Phosphate seriously inhibited the removal of As(V) while fluoride did not compete with As(V) even at an F/As molar ratio as high as 30, suggesting that the adsorption sites for As(V) and fluoride were different. Salinity, hardness, and other inorganic anions such as Cl(-), NO(3)(-), and SO(4)(2-) had no apparent effect on As(V) adsorption. Fourier transform infrared spectra of Ce-Fe adsorbent before and after As(V) adsorption demonstrated that M-OH groups plays an important role for As(V) ions removal in the adsorption mechanisms of Ce-Fe adsorbent.     

LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters

Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC-MS-MS. APs were separated by LC from APECs using an acetonitrile-water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS-MS fragment ions (219>133 and 147). 4n-NP shows the characteristic transition 219>106; it is well suited as internal standard. Nonylphenol ethoxylates NPE(n)Os (n=1-17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 microg l(-1) NPE1C in a WWTP effluent and 3.6 microg l(-1) NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 microg l(-1)). The predicted no-effect concentration (PNEC) for NP of 0.33 microg l(-1) for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.     

Congener-distribution patterns and risk assessment of polychlorinated biphenyls,dibenzo-p-dioxins and dibenzofurans in Korean human milk

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry in human milk samples from an urban and an industrial area in Korea. All PCB congeners were analyzed to characterize the congener distribution as well as to evaluate the toxic equivalent quotient (TEQ) values and the total concentration. In homologue distributions of PCBs, two distinct patterns were found. The mean concentrations of PCDD/Fs and PCBs were 15.13 and 5.64 TEQ pg/g fat (based on WHO TEF, 1997), respectively. The contamination in Korean human milk is comparable to that found in other countries. From these results a daily intake of 60 TEQ pg/kg/day for an infant was estimated. The assumptions were that the infant breast feeds for 1 year, has an average body weight of 10 kg during this period, and ingests 800 g/day of human milk containing a mean concentration of 20.84 TEQ (PCDD/Fs) pg/g fat (based on primipara mothers).     

Biomonitoring of airborne mercury with perennial ryegrass cultures

A biomonitoring network with grass cultures was established near a chlor-alkali plant and the mercury concentration in the cultures were compared with the average atmospheric total gaseous mercury (TGM). Biomonitoring techniques based on different exposure periods were carried out. When comparing the mercury concentration in the grass cultures, both the average atmospheric TGM concentration during exposure and the exposure time determined to a large extent the accumulation rate of TGM. The maximum tolerable level of mercury in grass (approximately equal to 110 microg kg(-1) DM) corresponds with an average TGM concentration of 11 ng m(-3) for 28 days exposure. The background concentrations in grass were on an average 15 microg kg(-1) DM and the effect detection limit (EDL) was 30 microg kg(-1) DM. This value corresponds with an average TGM concentration of 3.2 and 4.2 ng m(-3) for 28 and 14 days exposure, respectively, which is in turn the biological detection limit (BDL) of ambient TGM. Exposures for 7 days were less appropriate for biomonitoring.