Half-lives of tetra-, penta-, hexa-, hepta-, and octachlorodibenzo-p-dioxin in rats,monkeys, and humans--a critical review

The elimination half-lives (t1/2) in Sprague-Dawley rats for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 1,2, 3,7,8-pentachlorodibenzo-p-dioxin (PeCDD), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (HxCDD), 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) were estimated in long-term studies by Schlatter, Poiger and others. Furthermore, there are some published half-lives of TCDD in adult humans. The average half-life of TCDD in adult humans is approximately 2840 days, while in Sprague-Dawley rats the average t1/2 of TCDD is 19 days. The t1/2 of TCDD in humans is about 150 times that of rats. This factor was used to calculate the t1/2 values of the other polychlorinated dibenzo-p-dioxins (PCDDs) in humans from the rat data. Furthermore, the terminal t1/2 values of PCDDs in adult humans were calculated from the regression equation: logt1/2H = 1.34 logt1/2R + 1.25 which was recently established for 50 xenobiotics (t1/2H = terminal half-lives in days for humans, t1/2R = terminal half-lives in days for rats). The following terminal half-lives in adult humans were obtained: 12.6 years for 1,2,3,7,8-PeCDD, 26-45 years for 1,2,3,4,7,8-HxCDD, 80-102 years for 1,2,3,4,6,7,8-HpCDD and ca. 112-132 years for OCDD. These half-lives of PCDDs are critically compared with measured t1/2 values of PCDDs and other persistent organic pollutants in rats, monkeys and humans.     

Polychlorinated-naphthalenes, -biphenyls, -dibenzo-p-dioxins, -dibenzofurans and p,p'-DDE in bluefin tuna,swordfish, cormorants and barn swallows from Italy

Concentrations of p,p'-DDE, polychlorinated biphenyl congeners (PCBs), polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -naphthalenes (PCNs) were measured in bluefin tuna, swordfish, common cormorants, and barn swallows collected from Italy. Average concentrations of PCBs in livers of tuna, swordfish, cormorant, and swallows were 930, 745, 1420 and 1230 ng PCBs g-1, w.w. respectively. p,p'-DDE was found in tuna, swordfish, cormorant, and swallow livers at mean concentrations of 82, 135, 166 and 95 ng DDE g-1, w.w. respectively. PCNs were found in all the samples analyzed, although at concentrations less than those reported for biota from the Baltic Sea. PCBs, particularly, non-ortho coplanar PCBs accounted for 80-90% of the total TEQs in tuna and swordfish. Relative contribution of PCDDs/DFs to TEQs was greater in cormorants and swallows compared to that in fishes. PCDD/DF congeners accounted for up to 80 and 45% of the total TEQs in cormorants and swallows, respectively.     

Radionuclides (lead-210, polonium-210, thorium-230, and -232) and thorium and uranium in water, sediments, and fish from lakes near the city of Elliot Lake, Ontario, Canada

Radionuclides (210Pb, 210Po, 230Th, and 232Th) and chemical Th and U were measured in water, sediments, and fish tissues (bone, muscle, and gut contents of laketrout, Salvelinus namaycush, whitefish, Coregonus clupeaformis and Prosopium cylindraceum) from four lakes in a watershed affected by U mining and milling operations at Elliot Lake, Ontario, and from control lakes in an adjacent, non-industrialized, watershed. Radionuclide concentration ratios between tissue levels and sediment and water levels were calculated. Annual radionuclide intakes and resulting doses were estimated for humans consuming fish from the watershed. Bone 210Pb levels were higher (186 mBq g(-1) dry wt in laketrout and 230 mBq g(-1) dry wt in one lake whitefish) than in muscle (< 50 mBq g(-1) dry wt in all cases), and generally higher in fish from study lakes than from controls, but no consistent differences were observed among fish species. Similarly, 210Po levels were higher in bone (208 +/- 33 mBq g(-1), in laketrout) than muscle (maximum 26 +/- 4 mBq g(-1), in laketrout), and in study lake populations compared to controls. Laketrout 210Po bone concentrations were higher than previously reported in Canada. Levels of 230Th, 232Th, and Th were below detection limits (20 mBq g(-1), 0.05 microg g(-1)) in body tissues in all fish species. Bone levels of U (14.6 +/- 3.0 microg g(-1), in lake whitefish) were higher than in muscle (most < 0.05 microg g(-1), except 0.12 +/- 0.04 and 0.08 +/- 0.03 microg g(-1) in lake whitefish) in fish from waters affected by industrial activity. In control lakes, bone and muscle levels were lower and not significantly different from each other. Muscle levels did not vary consistently with location. Concentration of 210Pb and U was seen from water and 'gut' material (taken as a surrogate for diet) to bone in laketrout and whitefish, and of U from water to muscle in whitefish, but in no case from sediments to tissues. Human intakes of 210Pb, 210Po, 230Th, 232Th, and U from consuming one meal of fish (375 g) per week could, in aggregate, represent an annual effective dose < 15% of the public dose limit (5 mSv). Monitoring biota living near the decommissioned Elliot Lake U operations, especially of 210Pb levels in fish muscle, with further assessment of human doses attributable to local fish and other animals in the diet, should continue. Because radionuclide effects on fish health (and on other non-human organisms) are of increasing concern, neoplasms, malformations, and reproductive anomalies in local fish deserve examination.     

Lead,mercury, cadmium,chromium, nickel,copper, zinc,calcium, iron,manganese and chromium (VI) levels in Nigeria and United States of America cement dust

This study was aimed at investigating the relative abundance of heavy metals in cement dust from different cement dust factories in order to predict their possible roles in the severity of cement dust toxicity. The concentrations of total mercury (Hg), copper (Cu), chromium (Cr), cadmium (Cd), nickel (Ni), manganese (Mn), lead (Pb), iron (Fe) and chromium (VI) (Cr (VI)) levels in cement dust and clinker samples from Nigeria and cement dust sample from the United States of America (USA) were determined using graphite furnace atomic absorption (GFAAS), while Zn and Ca were measured by flame atomic absorption spectrophotometry (FAAS), and Cr (VI) by colorimetric method. Total Cu, Ni and Mn were significantly higher in cement dust sample from USA (p < 0.05), also, both total Cr and Cr (VI) were 5.4–26 folds higher in USA cement dust compared with Nigeria cement dust or clinker (p < 0.001). Total Cd was higher in both Nigeria cement dust and clinker (p < 0.05 and p < 0.001), respectively. Mercury was more in both Nigeria cement dust and clinker (p < 0.05), while Pb was only significantly higher in clinker from Nigeria (p < 0.001). These results show that cement dust contain mixture of metals that are known human carcinogens and also have been implicated in other debilitating health conditions. Additionally, it revealed that metal content concentrations are factory dependent. This study appears to indicate the need for additional human studies relating the toxicity of these metals and their health impacts on cement factory workers.     

Toxicity of carbaryl,diquat dibromide,and fluoranthene,individually and in mixture,to larval grass shrimp,Palaemonetes pugio

This study examined the toxicity of two pesticides (carbaryl and diquat dibromide) and one polycyclic aromatic hydrocarbon (fluoranthene), both singly and in mixture, to grass shrimp larvae (Palaemonetes pugio). These three chemicals are all present in coastal environments and can easily enter estuarine ecosystems. Fluoranthene was the most toxic chemical with a 96-h LC₅₀ value of 32.45 μ g/L, followed by carbaryl (43.02 μ g/L) and diquat dibromide (1624 μ g/L). In the chemical mixture tests, the binary carbaryl/diquat dibromide mixture and the ternary carbaryl/diquat dibromide/fluoranthene mixture had additive results.     

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)₂Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.     

Organochlorines, including chlordane compounds and their metabolites, in peregrine-falcon, prairie-falcon, and clapper-rail eggs from the USA

Four compounds present in technical chlordane (trans- and cis-nonachlor, and tentatively MC-2 and MC-5) and three metabolites of chlordane (heptachlor epoxide, oxychlordane, and U-4) were identified by GC/MS in peregrine-falcon (Falco peregrinus anatum) eggs. Levels of Heptachlor epoxide, oxychlordane, trans- and cis-chlordane, trans- and cis-nonachlor, MC-2, and MC-5 were quantified by GC/ECD in peregrine-falcon eggs from the US east coast, Colorado, and California; and in prairie-falcon (Falco mexicanus) and light-footed-clapper-rail (Rallus longirostris levipes) eggs from California. The eggs were collected between 1986 and 1989. Oxychlordane, heptachlor epoxide, trans- and cis-nonachlor, MC-2, and MC-5 were detected in every egg analyzed. Heptachlor, trans-, and cis-chlordane were either not detected, or present at low levels in the eggs. The highest Sigmachlordane levels were found in the East Coast peregrine-falcon eggs at a geometric mean (geom. mean) concentrations of 1800 microg/kg (ppb); the lowest levels of Sigmachlordane were found in the prairie-falcon eggs at a concentration of 120 microg/kg (geom. mean). Of the technical chlordane compounds measured, MC-2 bioaccumulated to the greatest degree. SigmaDDT levels in the falcons ranged from 11 000 microg/kg (geom. mean) in the Colorado samples to 8800 microg/kg (geom. mean) in the East Coast and California peregrines. SigmaDDT levels in the rail eggs were 3000 microg/kg (geom. mean). The highest SigmaPCB levels were found in the East Coast peregrine-falcon eggs at a concentration of 14 000 microg/kg (geom. mean); the lowest levels of SigmaPCB were found in the prairie-falcon eggs at a concentration of 350 microg/kg (geom. mean).     

Toxicity of carbaryl, diquat dibromide, and fluoranthene, individually and in mixture, to larval grass shrimp, Palaemonetes pugio

This study examined the toxicity of two pesticides (carbaryl and diquat dibromide) and one polycyclic aromatic hydrocarbon (fluoranthene), both singly and in mixture, to grass shrimp larvae (Palaemonetes pugio). These three chemicals are all present in coastal environments and can easily enter estuarine ecosystems. Fluoranthene was the most toxic chemical with a 96-h LC50 value of 32.45 microg/L, followed by carbaryl (43.02 microg/L) and diquat dibromide (1624 microg/L). In the chemical mixture tests, the binary carbaryl/diquat dibromide mixture and the ternary carbaryl/diquat dibromide/fluoranthene mixture had additive results.     

Occurrence of PCDD/F, PCB, PBDE, PFAS, and organotin compounds in fish meal, fish oil and fish feed

We analysed polychlorinated dibenzo-p-dioxins and furans (PCDD/F, dioxins), and polychlorinated biphenyls (PCB) in 13 fish meal, five fish oil, and seven fish feed samples. Polybrominated diphenyl ethers (PBDE), organotin compounds (OTC), and perfluoroalkylated substances (PFAS) were analysed in ten fish meal, two fish oil, and two fish feed samples. All measured TEQ concentrations of PCDD/F and PCB were below the maximum levels set by Directive 2002/32/EC. There was no correlation between concentrations of WHOPCDD/F-TEQ and indicator PCB in our samples. The most common congeners among PBDEs were BDE-47 and BDE-100. BDE-209 was present in five fish meals of the ten analysed. Tributyltin (TBT) was the predominant congener in all samples except in three fish meals, where monobutyltin (MBT) was the major congener. Perfluorooctane sulphonate (PFOS) was the predominant congener in six fish meals of the ten analysed. There was large variation in concentrations and congener distributions of the studied compounds between our samples. Our results underline a need to pay special attention to the origin and purity of feed raw material of marine origin.     

Distribution,origin, and transformation of metal and metalloid pollution in vegetable fields,irrigation water,and aerosols near a Pb-Zn mine

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind. Highlights ? Mining activities generated heavy metal pollution in fields around a Pb-Zn mine ? The elements from water and soils are strongly correlated ? Anglesite and cerussite are evidence of galena transformation into secondary minerals ? Particulate matter is an important transport carrier of pollution     

Levels of polychlorinated biphenyls, organochlorine pesticides, mercury, cadmium, copper, selenium, arsenic, and zinc in the harbour seal, Phoca vitulina, in Norwegian waters

Residue levels of the chlorinated hydrocarbons polychlorinated biphenyls (PCBs), total DDT, alpha-, beta- and gamma-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), and oxychlordane in blubber, and the elements mercury, cadmium, copper, selenium, arsenic, and zinc in liver, of 82 harbour seals, Phoca vitulina, were determined. The seals were found dead or dying in Norwegian waters during the disease outbreak caused by a morbilli virus in 1988. Of the chlorinated hydrocarbons, the highest concentrations were found of PCBs, which were 2-4 times higher than the total DDT concentrations. P,p'-DDE was the main contributor to the total DDT, and constituted about 80%. The PCB and total DDT concentrations ranged from 0.4-38 and 0.1-8.8 mg kg(-1), respectively. The mercury concentrations ranged from 0.1-89 mg kg(-1). Significantly higher mean levels of PCBs (13 mg kg(-1) and mercury (16 mg kg(-1)) were found in blubber and liver, respectively, of seals from the Southern coast of Norway, as compared to the corresponding mean levels in seals from the Oslofjord (8.8 and 4.1 mg kg(-1)), and at the Northwestern coast (5.8 and 7.9 mg kg(-1)), respectively. A significant positive correlation was found between the concentrations of selenium and mercury. When the seals were grouped according to sex and age, females of ageclass > 1 and pups of both sexes had significantly lower PCB and total DDT levels than males ageclass > 1. Significantly higher hepatic mercury levels were found in seals ageclass > 1 as compared to pups. Only low levels of the other organochlorines, cadmium and arsenic, were found. Copper and zinc were considered to be present at normal physiological levels. The present organochlorine and heavy metal concentrations gave no support to suggestions that organochlorines and heavy metal pollution may be directly involved in the observed seal deaths.     

A Comparison of Mass,Lead, Sulfate,and Nitrate Concentrations in a Field Study Using Dichotomous,Size-Selective,and Standard Hi-Vol Samplers

Air monitoring In the San Francisco Bay Area was carried out to measure outdoor community air concentrations of poly cyclic aromatic hydrocarbons (PAH) and mutagenlc activity (mutagenlclty) In participate organic matter (POM). Monitoring began In 1979 and Is currently conducted at six stations. PAH and mutagenlclty tests were performed on organic extracts prepared from high volume (hl-vol) filters composited every four months, by meteorological season. PAH were determined by high pressure liquid chromatography (HPLC) with fluorescence and ultraviolet detection. Mutagenlclty was measured In the Ames Salmonella bloas-say using strain TA98 with and without metabolic activation. The nine-year mean concentration of benzo(a)pyrene (BaP) was 0.4 ng/m³. The mutagenlcfty of this amount of BaP accounted for only about 0.2% of the observed mutagenicity In POM and other measured PAH accounted for even less. Concentrations of PAH and mutagenlclty were three to nine times higher during the winter than during other seasons. Year-to-year wintertime trends In several PAH were also seen. Early In the 1980s, winter concentrations of BaP and benzo (g,h,i)perylene Increased. However since the mld-1980’s, their concentrations have fallen. The decrease In PAH concentrations may be the result of an Increasing proportion of vehicles with relatively low organic emissions. In contrast to PAH, mutagenlcfty did not show significant year-to-year time trends.     

PCBs,PCNs, PCDD/Fs,PAHs and Cl-PAHs in air and water particulate samples--patterns and variations

Methodology for the determination of biologically active polychlorinated biphenyls (PCBs), non-ortho PCBs, polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) was used to investigate concentrations and patterns of certain chlorinated PAH (Cl-PAH) in source related samples using synthetic reference mixtures. Thus, in addition to the above mentioned compounds, mono-heptachlorosubstituted fluorenes, phenanthrenes/anthracenes and pyrenes/fluoranthenes (Cl-PAHs) were measured in vapour and particulate air samples from urban road tunnels, samples of settling particulate matter (SPM), and in bottom sediment samples from two point source locations (pulp and paper, and Mg-plant/Fe-Mn-smelter/chlor-alkali) and in the Baltic Sea. Concentrations in air samples followed: PAHs>PCBs>PCNs>non-ortho PCBs or Cl-PAHs>PCDD/Fs. SPM samples collected at increasing distance to the urban area of Stockholm showed: PAHs>PCBs>PCNs>PCDD/Fs>non-ortho PCBs or Cl-PAHs. For all compound groups there was a tenfold (Cl-PAHs fivefold) concentration decrease in SPM samples from highest levels in the urban water area to lowest levels at a distance of 26 km from city centre. PCB profiles of SPM showed similarities with combined profiles of Aroclor 1242 and 1254. PCN profiles of SPM showed similarities with combined profiles of Halowax 1099 and 1014. A correlation with concentration of all tested Cl-PAH and their corresponding parent PAH was found only for Cl-fluorene.     

Cadmium,chromium and lead contamination of Athene noctua,the little owl,of Bologna and Parma,Italy

A study was conducted to determine cadmium, chromium and lead concentrations in liver and brain of 52 little owls (Athene noctua) from two provinces of Emilia Romagna region, with the aim of furnishing indirect information concerning contamination of their habitat, also considering possible environmental dispersion of the metals. Metal analysis was performed by atomic absorption spectrophotometry with graphite furnace. Variance analysis with sampling area, gender and age shows that no statistical difference was found for gender, while a significant difference (P<0.05) was found for cadmium and lead, but not for chromium, when sampling areas and age were of concern. For all metals highest mean concentrations were found in liver (170 ppb for cadmium, 297 ppb for chromium and 312 ppb for lead). These levels can be considered as indicative of chronic exposure to low and "background" amounts of pollutants and they are of no toxicological concern, as they are always well below the toxic thresholds defined for each metal. The present study can be considered as a starting point for further analyses, aimed to the definition of any possible subtle effect (e.g. effects on enzymes activity) and of any possible correlation between levels of pollutants and appearance of possible adverse effects. It also furnished useful data for diagnostic cases and potentially for monitoring local contamination.     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.     

PCB, DDT, arsenic, and heavy metal (Cd, Cu, Pb, and Zn) concentrations in chameleon (Chamaeleo chamaeleon) eggs from Southwest Spain

This work presents the concentrations of twenty PCB congeners, p,p'-DDT, and its two main metabolites, p,p'-DDE, p,p'-TDE, As, Cd, Cu, Pb, and Zn found in common chameleon eggs from nine different nests located in Southwest Spain. Of the heavy metals and arsenic, Zn and Cu exhibited the highest concentrations in egg contents (ranging from 10100 to 12950 and from 567 to 706 ng g(-1) wet weight basis [w.w.], respectively) and eggshells (ranging from 5605 to 13290 ng g(-1)w.w. for Zn and from 1487 to 4361 ng g(-1)w.w. for Cu). Total PCB concentrations in egg contents ranged from 32 to 52 ng g(-1)w.w. and were higher than total dichlorodiphenylethanes concentrations (ranging from 0.67 to 1.9 ng g(-1)w.w., calculated as the sum of p,p'-DDT plus p,p'-DDE and p,p'-TDE). Comparison of the data from the present study with the data from a study conducted in 1997 revealed a large decrease in Pb concentration and a twofold increase in PCB concentrations. Taking into account all the pollutants investigated, the contamination level found in common chameleon eggs from Southwest Spain was generally lower than has been reported in the literature for eggs of different reptile species. However, it should be borne in mind that most of the data found in the literature refer to highly polluted areas.     

Chromium transport, oxidation, and adsorption in manganese-coated sand

We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (beta-MnO2)-coated sand. We find that beta-MnO2 effectively oxidizes Cr(III) to Cr(VI) and that the extent of oxidation is sensitive to changes in pH, pore water velocity, and influent concentrations of Cr(III). Cr(III) oxidation rates, although initially high, decline well before the supply of beta-MnO2 is depleted, suggesting that a reaction product inhibits the conversion of Cr(III) to Cr(VI). Rate-limited reactions govern the weak adsorption of each chromium species, with Cr(III) adsorption varying directly with pH and Cr(VI) adsorption varying inversely with pH. The breakthrough data on chromium transport can be matched closely by calculations of a simple model that accounts for (1) advective-dispersive transport of Cr(III), Cr(VI), and dissolved oxygen, (2) first-order kinetics adsorption of the reduced and oxidized chromium species, and (3) nonlinear rate-limited oxidation of Cr(III) to Cr(VI). Our work supplements the limited database on the transport of redox-sensitive metals in porous media and provides a means for quantifying the coupled processes that contribute to this transport.     

Effect of four alcohols on adsorption, desorption, and movement of cadmium, nickel, and zinc through soils

Miscible-displacement experiments were conducted to compare the effects of aqueous soil solutions with ethyl alcohol, ethylene glycol, diethylene glycol, and triethylene glycol on the movement of metals through soils. Aqueous or alcohol solutions containing 1 mM each Cd, Ni, and Zn and 5 mM Ca were perfused through columns containing River Sand, Canelo loam (Canelo 1) or Mohave sandy clay loam (Mohave scl) until effluent metal concentrations (C) equaled influent concentrations (C₀) or CC₀⁻¹ = 1. In general, the order of sorption was Zn > Ni > Cd in aqueous-perfused columns, while in alcohol-perfused columns sorption of Ni Cd ≥ Zn. In comparison to aqueous solutions, alcohols reduced total metal sorption by at least 25%. Metal sorption was best correlated to cation exchange capacity of the soil, sorption of metals being greatest in the Mohave scl and least in the River Sand. After CC₀⁻¹ = 1 was reached, columns were leached with deionized water. While leaching did not affect the sorption of metals in columns which had been perfused with aqueous solvents, sorption behavior of metals changed significantly in columns which had been perfused with alcohol solvents. Leaching caused desorption of 5 to 30% of the sorbed Ni. In general, Cd was desorbed (up to 45%) from the soils tested. The exceptions were River Sand columns perfused with diethylene and triethylene glycol in which additional Cd was sorbed to the soil from the soil solution. Additional Zn was sorbed in all columns tested with the exception of the Canelo 1 column perfused with ethyl alcohol.     

Removal of toxic ions (chromate, arsenate, and perchlorate) using reverse osmosis, nanofiltration, and ultrafiltration membranes

Rejection characteristics of chromate, arsenate, and perchlorate were examined for one reverse osmosis (RO, LFC-1), two nanofiltration (NF, ESNA, and MX07), and one ultrafiltration (UF and GM) membranes that are commercially available. A bench-scale cross-flow flat-sheet filtration system was employed to determine the toxic ion rejection and the membrane flux. Both model and natural waters were used to prepare chromate, arsenate, and perchlorate solutions (approximately 100 μg L⁻¹ for each anion) in mixtures in the presence of other salts (KCl, K₂SO₄, and CaCl₂); and at varying pH conditions (4, 6, 8, and 10) and solution conductivities (30, 60, and 115 mS m⁻¹). The rejection of target ions by the membranes increases with increasing solution pH due to the increasingly negative membrane charge with synthetic model waters. Cr(VI), As(V), and rejection follows the order LFC-1 (>90%) > MX07 (25–95%)  ESNA (30–90%) > GM (3–47%) at all pH conditions. In contrast, the rejection of target ions by the membranes decreases with increasing solution conductivity due to the decreasingly negative membrane charge. Cr(VI), As(V), and rejection follows the order CaCl₂ < KCl  K₂SO₄ at constant pH and conductivity conditions for the NF and UF membranes tested. For natural waters the LFC-1 RO membrane with a small pore size (0.34 nm) had a significantly greater rejection for those target anions (>90%) excluding (71–74%) than the ESNA NF membrane (11–56%) with a relatively large pore size (0.44 nm), indicating that size exclusion is at least partially responsible for the rejection. The ratio of solute radius (r_i,s) to effective membrane pore radius (r_p) was employed to compare ion rejection. For all of the ions, the rejection is higher than 70% when the r_i,s/r_p ratio is greater than 0.4 for the LFC-1 membrane, while for di-valent ions (, , and ) the rejection (38–56%) is fairly proportional to the r_i,s/r_p ratio (0.32–0.62) for the ESNA membrane.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.