Markers of oxidative stress and toxicant exposure among young waterpipe smokers in the USA

Waterpipe (aka hookah) tobacco smokers are exposed to toxicants that can lead to oxidative DNA and RNA damage, a precursor to chronic disease formation. This study assessed toxicant exposure and biomarkers of DNA [8-oxo-7, 8-dihydro-2′-deoxyguanosine (8-oxodG)] and RNA [8-oxo-7,8-dihydroguanosine (8-oxoGuo)] oxidative damage during smoking of flavored and non-flavored waterpipe tobacco. Thirty waterpipe smokers completed two counterbalanced 2-h lab waterpipe smoking sessions (flavored vs. non-flavored waterpipe tobacco). Urinary concentrations of 8-oxodG and 8-oxoGuo and expired carbon monoxide (eCO) were measured before and after the smoking sessions. A significant increase in the urinary concentrations of 8-oxodG (from 2.12 ± 0.83 to 2.35 ± 0.91 ng/mg creatinine, p = 0.024) and 8-oxoGuo (from 2.96 ± 0.84 to 3.45 ± 0.76 ng/mg creatinine, p = 0.003) were observed after smoking the non-flavored and flavored waterpipe tobacco, respectively. Our results also showed that the mean ± SD of eCO increased significantly after smoking the flavored (from 1.3 ± 1.1 to 20.3 ± 23.6 ppm, p < 0.001) and non-flavored waterpipe tobacco (from 1.8 ± 1.2 to 24.5 ± 26.1 ppm, p < 0.001). There were no significant differences in the means of 8-oxodG (p = 0.576), 8-oxoGuo (p = 0.108), and eCO (p = 0.170) between the flavored and non-flavored tobacco sessions. Smoking non-flavored and flavored waterpipe tobacco leads to oxidative stress and toxicant exposure. Our findings add to the existing evidence about the adverse effects of waterpipe tobacco smoking (WTS) and the need for strong policies to inform and protect young people from the risks of WTS.

     

Evaluation of CO exposure in active smokers while smoking using breath analysis technique

The current study evaluated the personal CO exposure of active smokers while smoking under controlled conditions, decay rate of CO in the body following active smoking, and CO accumulation in the body from repeated active smoking using a novel device for the direct measurement of alveolar breath CO. Prior to this evaluation, the proposed alveolar CO measurement device was successfully evaluated as regards the effect of humidity, CO recovery, carryover effect, and in comparison with the bag sampling method. The breath concentrations prior to and after a single cigarette were measured using a repeated measure design. Under the controlled conditions employed in the present study, active smoking was found to cause a significant body burden of CO. The post-exposure breath CO level was 1.6-2.0 times higher than the background breath level, depending on the subject and cigarette brand. In addition, the pre- and post-exposure breath concentrations were both significantly different among the subjects, yet the ratios of post-exposure to pre-exposure breath concentrations did not differ significantly between the different cigarette brands. The time-series alveolar breath concentrations measured following active smoking showed that the post-exposure alveolar CO concentrations decreased slowly even in the early phase of the decay curves, indicating a mono-compartment uptake and elimination model for the human body. The half-lives estimated in the present study (301, 315, and 385 min) were longer than or comparable to those in previous studies. The breath measurements prior to and after repeated active smoking exhibited a significant increasing trend for both the pre- and post-exposure concentrations. The changes in the pre- and post-exposure breath CO concentrations with repeated smoking ranged from 7% to 23% and from 10% to 15%, respectively, with half-hour intervals between cigarettes, and from 4% to 11% and from 6% to 8%, respectively, with hour intervals between cigarettes. Accordingly, most of the current results indicated that CO was accumulated in the human body with repeated active smoking.     

Secondhand smoke exposure at home and public places among smokers and non-smokers in India: findings from the Global Adult Tobacco Survey 2016–17

Environmental Science and Pollution Research - Secondhand smoke (SHS) accounts for 0.9 million deaths and 24 million disability adjusted life years (DALYs) annually. Nearly 30% of adults in India...     

Frequency of PPAR-γ, FTO and ABCC8 genetic variation in Pakistani cardiovascular smokers

Environmental Science and Pollution Research - Smoking is considered as one of the major reasons behind genetic variations in cardiometabolic disorders. However, effect of nicotine via smoking on...     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Development of methane emission factors for Indian paddy fields and estimation of national methane budget

A state-wise assessment of methane (CH(4)) budget for Indian paddies, based on a decadal measurement data across India is presented for the calendar year (CY) 1994, the base year for India's Initial National Communication (NATCOM) to the United Nations Framework Convention on Climate Change (UNFCCC), along with national trend from CY 1979 to 2006. The NATCOM CH(4) emission factors (EFs) for Indian paddy cultivation areas, generally having less than 0.7% of soil organic carbon (SOC), have been estimated as 17.48+/-4 g m(-2) for irrigated continuously flooded (IR-CF), 6.95+/-1.86 g m(-2) for rain-fed drought prone (RF-DP), 19+/-6 g m(-2) for rain-fed flood prone (RF-FP) and deep-water (DW), 6.62+/-1.89 g m(-2) for irrigated intermittently flooded single aeration (IR-IF-SA) and 2.01+/-1.49 g m(-2) for IR-IF multiple aeration (MA) paddy water regimes. The state-wise study for 1994 has indicated national CH(4) budget estimate of 4.09+/-1.19 Tg y(-1) and the trend from 1979 to 2006 was in the range of 3.62+/-1 to 4.09+/-1.19 Tg y(-1). Four higher emitting or "hot spot" states (West Bengal, Bihar, Madhya Pradesh and Uttar Pradesh) have accounted for 53.9% of total CH(4) emission with RF-FP paddy water regime as the major contributor. CH(4) emissions were enhanced by factors such as SOC ( approximately 1.5 times due to increase in SOC by approximately 1.8 times), paddy cultivars (approximately 1.5 times), age of seedlings (approximately 1.4 times), and seasons (approximately 1.8 times in Kharif or monsoon than in Rabi or winter season).     

A technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).     

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.     

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.     

Uptake and loss of dissolved 109Cd and 75Se in estuarine macroinvertebrates

Semaphore crabs (Heloecius cordiformis), soldier crabs (Mictyris platycheles), ghost shrimps (Trypaea australiensis), pygmy mussels (Xenostrobus securis), and polychaetes (Eunice sp.), key benthic prey items of predatory fish commonly found in estuaries throughout southeastern Australia, were exposed to dissolved (109)Cd and (75)Se for 385 h at 30 k Bq/l (uptake phase), followed by exposure to radionuclide-free water for 189 h (loss phase). The whole body uptake rates of (75)Se by pygmy mussels, semaphore crabs and soldier crabs were 1.9, 2.4 and 4.1 times higher than (109)Cd, respectively. There were no significant (P>0.05) differences between the uptake rates of (75)Se and (109)Cd for ghost shrimps and polychaetes. The uptake rates of (109)Cd and (75)Se were highest in pygmy mussels; about six times higher than in soldier crabs for (109)Cd and in polychaetes for (75)Se - the organisms with the lowest uptake rates. The loss rates of (109)Cd and (75)Se were highest in semaphore crabs; about four times higher than in polychaetes for (109)Cd and nine times higher than in ghost shrimps for (75)Se - the organisms with the lowest loss rates. The loss of (109)Cd and (75)Se in all organisms was best described by a two (i.e. short and a longer-lived) compartment model. In the short-lived, or rapidly exchanging, compartment, the biological half-lives of (75)Se (16-39 h) were about three times greater than those of (109)Cd (5-12h). In contrast, the biological half-lives of (109)Cd in the longer-lived, or slowly exchanging compartment(s), were typically greater (1370-5950 h) than those of (75)Se (161-1500 h). Semaphore crabs had the shortest biological half-lives of both radionuclides in the long-lived compartment, whereas polychaetes had the greatest biological half-life for (109)Cd (5950 h), and ghost shrimps had the greatest biological half-life for (75)Se (1500 h). This study provides the first reported data for the biological half-lives of Se in estuarine decapod crustaceans. Moreover, it emphasises the importance of determining metal(loid) accumulation and loss kinetics in keystone prey items, which consequently influences their trophic transfer potential to higher-order predators.     

QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P(L)) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P(L) predicted by models used varied between -3.94 to -2.66 for Mono-; -4.85 to -2.97 for Di-; -5.18 to -3.17 for Tri-; -6.02 to -3.77 for Tetra-; -6.64 to -4.64 for Penta-; -7.36 to -4.76 for Hexa-; -7.54 to -5.79 for Hepta-; -7.75 to -6.64 for Octa-; -7.89 to -7.44 for Nona-Ct-Abs; and -8.09 and -8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P(L) -4 to -2) and low (log P(L) < -4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

Diffusion of HTO, 36Cl- and 125I- in Opalinus Clay samples from Mont Terri. Effect of confining pressure

Diffusion coefficients (T=23 +/- 2 degrees C) and accessible porosities for HTO, 36Cl(-) and 125I(-) were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na(+) and Cl(-) as the main components (I=0.42 M). The measured values of the effective diffusion coefficients (D(e)) and rock capacity factors (alpha) are: D(e)=1.2-1.5 x 10(-11) m(2) s(-1) and alpha=0.09-0.11 for HTO, D(e)=4.0-5.5 x 10(-12) m(2) s(-1) and alpha=0.05 for 36Cl(-) and D(e)=3.2-4.6 x 10(-12) m(2) s(-1) and alpha=0.07-0.10 for 125I(-). For non-sorbing tracers (HTO, 36Cl) the rock capacity factor alpha is equal to the diffusion-accessible porosity epsilon. The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of approximately 17% for HTO, approximately 28% for 36Cl(-) and approximately 30% for 125I(-). Moreover, the diffusion coefficients for 36Cl(-) and 125I(-) are smaller than for HTO, which is consistent with an effect arising from anion exclusion. The diffusion coefficients of HTO and 125I(-) measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Estimation of K(OA) values of 209 polychlorinated trans-azobenzenes by PM6 and DFT methods

The octanol-air partition coefficients (K(OA)) of all 209 PCt-ABs were determined computationally to fill gaps on their environmentally relevant physical and chemical properties. These properties have been determined using two computational approaches: the semi-empirical quantum chemistry method for property parameterization (PM6) of the molecular orbital package (MOPAC) and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set in Gaussian 03 software and artificial neural network (ANN) predicting abilities. Both computational methods enabled estimation of log K(OA) partition coefficients of PCt-ABs with a similar accuracy and precision. The PM6 method compared to DFT was highly superior because it requires much less time, manpower and cost of hardware. The determined log K(OA) values of the investigated PCt-ABs for standard condition (25 °C) varied between 8.30 and 8.75 for Mono-; 8.71 and 9.92 for Di-; 9.58 and 10.72 for Tri-; 10.11 and 11.34 for Tetra-, 10.83 and 11.85 for Penta-; 11.24 and 12.36 for Hexa-; 11.87 and 12.66 for Hepta-; 12.31 and 12.97 for Octa-; 12.89 and 13.21 for Nona-Ct-ABs; and 13.17- and 13.49 for Deca-Ct-AB. PCt-ABs, in view of these log K(OA) values, can be classified as compounds of relatively low (Mono-, Di- and some of Tri- Ct-ABs with values of log K(OA) around 8 to 10) environmental mobility (most of Tri- to Nona-Ct-ABs and Deca-Ct-AB homologues with values of log K(OA) >10), and with a potential to be adsorbed by soil particles.     

A simple spectrophotometric method for the determination of cobalt in industrial, environmental, biological and soil samples using bis(salicylaldehyde)orthophenylenediamine

Bis(salicylaldehyde)orthophenylenediamine (BSOPD) has been proposed as new analytical reagent for the direct non-extractive spectrophotometric determination of cobalt. It reacts with cobalt in slightly acidic (0.0002-0.001 M H(2)SO(4)) 50% 1,4-dioxanic medium to form a red-orange chelate with a molar ratio 1:1. The reaction is instantaneous and the maximum absorbance was obtained at 458 nm and remains constant for over 24h. The average molar absorption coefficient and Sandell's sensitivity were found to be 1.109 x 10(4)l mol(-1)cm(-1) and 20 ng cm(-2) of Co(II), respectively. Linear calibration graph was obtained for 0.1-15 mg l(-1) of Co(II) with a correlation coefficient value of 0.995 for Co-BSOPD complex. Large excess of 44 cations, anions and complexing agents do not interfere in the determination. The method was successfully used in the determination of cobalt(II) from synthetic mixture and certified reference materials for the purpose of validating the method and the results of analyses were found to be excellent agreement with those of actual values. This developed method was also used for determination of cobalt in some environmental waters (potable and polluted), biological (blood and urine) and soil samples and solution containing both cobalt(II) and cobalt(III). The results of the proposed method for biological samples were comparable with AAS and were found to be in good agreement. The method has high precision and accuracy (s=+/-0.01 for 0.5 mg l(-1)).     

Constructed wetlands treating highway runoff in the central Mediterranean region

Two free water surface (FWS) and two subsurface flow (SSF) pilot-size constructed wetlands treating highway runoff (HRO) were monitored over a period of two years (September 2005-August 2007). One FWS and one SSF were designed with a hydraulic retention time (HRT) of 12h, named FWS12 and SSF12, respectively, with each one capable of treating a maximum HRO of 12.6 m(3) d(-1). The other couple, named FWS24 and SSF24, respectively, was designed with an HRT of 24h, with each receiving a maximum HRO of 6.3 m(3) d(-1). The influent flowed from a highway section with a total surface 2752 m(2) on the island of Crete, Greece, in the heart of the South-Central Mediterranean region. Influent and effluent were monitored for COD, TSS, total N (TN), NO(3)(-) and total P (TP) concentrations. Furthermore, removal efficiencies were examined for heavy metals (Cu, Ni, Pb, Zn) for both years, while polycyclic aromatic compounds (PAHs) were examined for the period between September 2006 and August 2007. The influent had a two-year average COD value of 101 mg l(-1), whereas the mean values for TSS, TN, N-NO(3)(-) and TP were 203, 4.30, 1.25 and 4.17 mg l(-1), respectively. For Cu, Ni, Pb and Zn the respective two-year mean influent concentrations were 56, 114, 49 and 250 microg l(-1). Mean concentration of total PAHs in runoff (summation operator PAHs, 16 compounds) were 12.01 microg l(-1). The performance among the four beds was not significantly different according to ANOVA analysis followed by Tukey test (at p<0.05) for almost all the above physicochemical parameters, suggesting that all systems performed in a similar way. All studied systems, achieved a mean of two-year removal efficiencies of 47% for COD, 89% for TSS, 49% for TN, 58% for N-NO(3)(-), 60% for TP, 47% for Cu, 23% for Ni, 33% for Pb, 61% for Zn and 59% for summation operator PAHs (16 compounds).     

Levels, distributions and profiles of polychlorinated biphenyls in surface soils of Dalian, China

Surface soil (0-5cm) samples from 14 sampling sites including rural and urban areas of Dalian, a coastal city in Liaoning Province, China, were collected and analyzed for 84 polychlorinated biphenyls (PCBs). Total 57 PCB congeners were identified and mean concentration of total PCBs among all the sites was 2.8mugkg(-1) dry weight (dw) with a range of 1.3 (rural site) to 4.8mugkg(-1)dw (urban site). For the urban sites, total PCB concentrations in the soil samples collected in industrial area are highest, followed by those from business/residential sites and the garden sites, but the differences are not significant. Higher percentage of lighter weighted molecular PCBs were found in the rural site than urban sites in Dalian, possibly indicating the "urban fractionation effect". Total seven dioxin-like PCBs (CB-77, 81, 105, 114, 118, 123, and 126) have been found in Dalian soils and the mean concentration (in mugkg(-1)dw) among all the sites of CB-105 (0.17) is higher than any other dioxin-like PCBs, followed by that for CB-81 (0.14) and for 118 (0.06). No significant correlation relationship between the concentrations of dioxin-like PCBs and those of total PCBs was found. The toxic equivalency (TEQ) concentrations (in ngkg(-1)dw) of these seven dioxin-like PCBs in 14 soil samples range from 0.006(7) to 4.885(7) (with a mean 1.372(7)) for humans and mammals, from 0.001(7) to 0.37(7) (with a mean 0.14(7)) for fish, and from 0.01(7) to 31.47(7) (with a mean 17.23(7)) for birds.     

Bioaccumulation and critical body residue of PAHs in the amphipod,Diporeia spp: additional evidence to support toxicity additivity for PAH mixtures

Polycyclic aromatic hydrocarbons (PAHs) are considered to act additively when exposed as congener mixtures. Additive internal concentrations at the site of toxic action is the basis for recent efforts to establish a sum PAH guideline for sediment-associated PAH toxicity. This study determined the toxicity of several PAH congeners on a body residue basis in Diporeia spp. These values were compared to the previously established LR(50) value for a PAH mixture based on the molar sum of PAH congeners and demonstrated similar LR(50) values for individual PAH. These results support the contention that the PAH act at the same molar concentration whether present as individual compounds or in mixture. Aqueous exposures were conducted for 28 d, and the water was exchanged daily to maintain the exposure concentration. The concentration in the exposures declined by an average of 22% between water exchanges across all compounds, and ranged from 11% to 32%. The toxicokinetics were determined using both time-weighted-average (TWA) and time-variable water concentrations and were not statistically different between the two source functions. Toxicity was determined for both mortality and immobility (failure to swim on prodding) and on both a TWA water concentration and a body residue basis. The LC(50) values ranged from 1757 microg l(-1) for naphthalene after 10 d exposure to 79.1 microg l(-1) for pyrene after 28 d exposure, and the EC(50) ranged from 1587 microg l(-1) for naphthalene after 10 d exposure to 38.2 microg l(-1) for pyrene after 28 d exposure. The LR(50) values for all congeners at all lengths of exposure were essentially constant and averaged 7.5+/-2.6 micromol g(-1), while the ER(50) for immobility averaged 2.6+/-0.6 micromol g(-1). The bioconcentration factor declined with increasing exposure concentration and was driven primarily by a lower uptake rate with increasing dose, while the elimination remained essentially constant for each compound.     

Estimation of selected physicochemical properties for methylated naphthalene compounds

Liquid aqueous solubility (S(w,L)), octanol/water partition coefficients (K(ow)), liquid vapor pressure (P(v,L)), and Henry's law constants (H(c)) were estimated for 20 methylated naphthalenes ranging from monomethyl to tetramethylnaphthalenes. Chromatographic methods were used for the estimation. Chromatographic retention measurements were conducted for 11 reference compounds and regressions were fit between the retention indices and the physicochemical properties. HPLC octadecylsilyl column with acetonitrile/water eluent was used for the estimation of S(w,L) and K(ow). Two GC columns, HP5-MS and a more hydrophobic HP-1, were tested for the estimation of P(v,L). Measured retention indices for the methylated naphthalenes were entered to the regression equations to calculate the physicochemical properties for these compounds. Literature values, where available, were used to validate the calculated values. The method accurately estimated the physicochemical properties. Estimated S(w,L) and P(v,L) decreased with the number of methyl groups. K(ow) increased with the number of methyl groups. There was no obvious relation between H(c) and the number of methyl groups. Log S(w,L) ranged from 0.885 for 1,2,5,6-tetramethylnaphthalene to 2.269 for 1-methylnaphthalene (mmol/m(3)). Log K(ow) varied from 3.89 for 1-methylnaphthalene to 4.95 for 1,2,5,6-tetramethylnaphthalene. Log P(v,L) ranged from -0.983 for 1,2,5,6-tetramethylnaphthalene to 0.789 for 2-methylnaphthalene (Pa). Log H(c) varied from 1.03 for 1,4,5-trimethylnaphthalene to 1.73 for 2,6-dimethylnaphthalene (Pa m(3)/mol). There were no apparent effects of GC column hydrophobicity on the accuracy of the results. Estimation of S(w,L) and K(ow) based on GC retention indices was not as accurate as with HPLC. Comparison of the estimated values with values predicted by EPIWIN indicated that EPIWIN is useful in giving order-of-magnitude prediction of physicochemical properties.