Effect of fulvic acid on the sorption of Cu and Pb onto gamma-Al2O3

This work investigated the adsorption of Cu and Pb at the surface of gamma-Al(2)O(3) in the presence of fulvic acid to address the significance of dissolved organic matters on metal partitioning. Fulvic acid, obtained from International Humic Substance Society, represented dissolved organic matter. Fulvic acid concentrations employed herein were 1, 5, and 10 mg C/L, which simulated the relevant environmental conditions. Ion selective electrodes were employed to ascertain free Cu and Pb measurements. The maximum adsorption of 10mg C/L fulvic acid on gamma-Al(2)O(3) was 5 x 10(-2)mgC/mg gamma-Al(2)O(3). Fulvic acid promoted Cu adsorption in low pH conditions. The effects of fulvic acid on Pb adsorption were similar to those of Cu. The conditional stability constants of sorbed fulvic acids with Cu and Pb were determined to be in the order of 4 to 6 (log K). Cu and Pb species were modeled in heterogeneous systems using triple-layer model. Simulation results indicated that metal species are dominantly in complexation with fulvic acid, both in solution and at the gamma-Al(2)O(3) surface.     

Comparative study of simultaneous removal of As, Cu, and Pb using different combinations of electrokinetics with bioleaching by Acidithiobacillus ferrooxidans

Different designs of electrokinetics were applied to simultaneously remove arsenic, copper, and lead from contaminated soils. Single electrokinetics (control) resulted in superior removal efficiencies for Cu (73.5%) and Pb (88.5%), though the removal of As (3.11%) was relatively little. Sequential bioelectrokinetics of bioleaching with Acidithiobacillus ferrooxidans and electrokinetics enhanced the removal of As (25%), while Pb exhibited a significant decrease in removal efficiency (10.6%), due to the formation of insoluble compounds. In order to improve the overall performance, integrated bioelectrokinetics was designed by inoculating A. ferrooxidans into the electrolyte after 5 or 15 days of electrokinetics. Lead (75.8%) and copper (72%) were effectively removed through electrokinetics, after which arsenic (35%) was more efficiently removed by bioleaching-enhanced electrokinetics. A pilot-scale experiment indicated that integrated bioelectrokinetics is an effective means of remediation of soils contaminated with multiple heavy metals and arsenic.     

Multiple site study of recent atmospheric metal (Pb, Zn and Cu) deposition in the NW Iberian Peninsula using peat cores

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~ 1850 AD), concentration profiles of Pb, Zn and Cu were determined in four ²¹⁰Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128 μg g⁻¹ and 128 to 231 μg g⁻¹, respectively) and 3.5 for Cu (11 to 37 μg g⁻¹). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329 μg cm⁻² for Pb, 198 to 625 μg cm⁻² for Zn and 22 to 69 μg cm⁻² for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced ²¹⁰Pb accumulation and the interpretation of the inventory ratios (²¹⁰Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX^th century to maximum values in the second half of the XX^th century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22 mg m⁻² yr⁻¹ (mean of 18 ± 1 mg m⁻² yr⁻¹), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52 mg m⁻² yr⁻¹ in 1989-1996, and from 4 to 9 mg m⁻² yr⁻¹ in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess ²¹⁰Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records.     

Air pollution and meteorological processes in the growing dryland city of Urumqi (Xinjiang, China)

Seven years (2000-2006) of monthly PM₁₀ (particulate matter, d ≤ 10 μm), SO₂, and NO₂ concentrations are reported for Urumqi, the capital of Xinjiang in NW China. Considerably high mean annual concentrations have been observed, which ranged between 150 and 240 μg m^− 3 (PM₁₀), 31 and 50 μg m^− 3 (NO₂), and 49 and 160 μg m^− 3 (SO₂). The shapes of seasonal variation of all pollutants were remarkably similar; however, winter/summer ratios of concentrations were quite different for PM₁₀ (2-3) and NO₂ (≈ 4) compared to SO₂ (up to 30). Very high consumption rates of fossil fuels for energy generation and domestic heating are mainly responsible for high annual pollution levels, as well as the (very) high winter/summer ratios. Detailed analysis of the 2000-2006 records of Urumqi's meteorological data resulted in inter-annual and seasonal frequency distributions of (a) (surface) inversion events, (b) heights of surface inversions, (c) stability classes of Urumqi's boundary layer, and (d) the “Air Stagnation Index (ASI)”. Urumqi's boundary layer is shown to be characterized by high mean annual and seasonal frequencies of (surface) inversions and by the dominance of stable dispersion classes. A further outcome of the meteorological analysis is the proof of Urumqi's strong diurnal wind system, which might have particularly contributed to the stabilization of the nocturnal boundary layer. Annual and seasonal variations of pollutant's concentrations are discussed in the context of occurrences of inversions, boundary layer, stability classes, and ASI. The trend of Urumqi's air pollution indicates a strong increase of mean annual concentrations 2000-2003, followed by a slight increase during 2003-2006. These are in strong contrast to (a) the growth of Urumqi's fleet of motor vehicles and (b) to the growing number of stable regimes of Urumqi's boundary layer climate during same period. It is concluded that the (regional and) local administrative technical countermeasures have efficiently lowered Urumqi's air pollution levels.     

Cadmium solubility in paddy soils: effects of soil oxidation, metal sulfides and competitive ions

Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled “reaction cell” experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake.     

Sub-cellular partitioning of Zn, Cu, Cd and Pb in the digestive gland of native Octopus vulgaris exposed to different metal concentrations (Portugal)

Concentrations of Zn, Cu, Cd and Pb and their sub-cellular distributions were determined in composite samples of digestive glands of the common octopus, Octopus vulgaris caught from two areas of the Portuguese coast characterised by contrasting metal contamination. Minor contents of Zn (1%), Cu (2%), Cd (6%) and Pb (7%) were found in the insoluble fraction, consisting of nuclei, mitochondria, lysosomes and microsome operationally separated from the whole digestive gland through a sequential centrifugation. A tendency for linear relationships between metal concentrations in nuclei, mitochondria, lysosomes and whole digestive gland was observed. These relationships suggest that despite low metal content organelles responded to the increasing accumulated metals, which means that detoxifying mechanism in cytosol was incomplete. Poorer correlations between microsome and whole digestive gland did not point to metal toxicity in the analysed compartments. However, the high accumulated Cd indicated that O. vulgaris is an important vehicle of this element to its predators in the coastal environment.     

Internal convective heat transfer modeling: Critical review and discussion of experimentally derived correlations

Heat is transferred through building envelopes by conduction, radiation, and convection. Of these, convective heat transfer is often the weakest ‘link’ in the overall heat transfer model. While conduction and radiation heat transfer are supported by well-established analytical and numerical models, the treatment of convection is much less rigorous. Convection modeling involves solution of fluid dynamics problems in which the complexity of an enclosed space's geometry and the diversity of indoor airflow patterns require many fit-for-purpose convection correlations. These must take into account specifics of the space and of the heating ventilation and air-conditioning (HVAC) system. This paper provides an overview of the current knowledge on the modeling of convective heat transfer in load calculation and building energy simulation programs. The paper also discusses various issues related to the robustness of convection coefficient correlations, and reports on new experiments conducted to test the sensitivity of existing convection correlations. The discussed issues relate to: (1) the non-uniformity of the indoor temperature field; (2) the selection of a proper characteristic dimension; (3) the effect of adiabatic and non-adiabatic obstructions in the zone; and (4) the impact of airflow disturbance.     

Visibility, air quality and daily mortality in Shanghai, China

This study was designed to assess the association between visibility and air quality, and to determine whether the variations in daily mortality were associated with fluctuations in visibility levels in Shanghai, China. Mortality data were extracted from the death certificates, provided by Shanghai Municipal Center of Disease Control and Prevention, and visibility data were obtained from Shanghai Municipal Bureau of Meteorology. Air quality data (PM₁₀, PM_2.5, PM_10-2.5, SO₂, NO₂ and O₃) were obtained from Shanghai Environmental Monitoring Center. Generalized additive model (GAM) with penalized splines was used to analyze the mortality, visibility, air pollution, and covariate data. Among various pollutants, PM_2.5 showed strongest correlation with visibility. Visibility, together with humidity, was found appropriate in predicting PM_2.5 (R-squared: 0.64) and PM₁₀ (R-squared: 0.62). Decreased visibility was significantly associated with elevated death rates from all causes and from cardiovascular disease in Shanghai; one inter-quartile range (8 km) decrease in visibility corresponded to 2.17% (95%CI: 0.46%, 3.85%), 3.36% (95%CI: 0.96%, 5.70%), and 3.02% (95%CI: − 1.32%, 7.17%) increase of total, cardiovascular and respiratory mortality, respectively. The effect estimates using predicted PM_2.5 and PM₁₀ concentrations were similar to those assessed using actual concentrations. This is the first study in Mainland China assessing the association between visibility and adverse health outcomes. Our findings suggest the possibility of using visibility as a surrogate of air quality in health research in developing countries where air pollution data might be scarce and not routinely monitored.     

Remediation of PAHs in a saline-alkaline soil amended with wastewater sludge and the effect on dynamics of C and N

Contamination of soil with hydrocarbons occurs frequently and organic material, such as sludge, is often applied to accelerate their dissipation. Little is known, however, how sludge characteristics affect removal of polycyclic aromatic hydrocarbons (PAHs) from alkaline-saline soil. Soil of the former lake Texcoco with pH 9 and electrolytic conductivity 7 dS m(-1) was contaminated with phenanthrene and anthracene and amended with sludge, sterilized sludge, sludge adjusted to maintain pH in contaminated soil or glucose plus an inorganic N and P source while emission of CO2 and concentrations of NH4+, NO3-, NO2-, extractable P, phenanthrene and anthracene were monitored in an aerobic incubation experiment of 112 days. An agricultural soil from Acolman treated in the same way served as control. Contaminating the Texcoco soil increased emission of CO2 significantly, but not in the Acolman soil. After 112 days, the largest concentration of anthracene and phenanthrene was found in the Acolman soil added with glucose and the lowest in the sludge-amended soil. The largest concentration of anthracene in the Texcoco soil was found in soil added with sterile sludge and the lowest in the sludge-amended soil. The largest concentration of phenanthrene in the Texcoco soil was found in the glucose-amended soil and the lowest in the sludge-amended soil. It was found that addition of sludge removed more phenanthrene, but not anthracene from soil compared to the unamended contaminated soil, glucose inhibited dissipation of PAHs while microorganisms in the sludge contributed to their removal, and adjustment of soil pH had no effect. Organic material can be used to accelerate removal of hydrocarbons from soil, but the effect is controlled by soil type, contaminant and organic material characteristics.     

The effects of phytophagous insects on water and soil nutrient concentrations and fluxes through forest stands of the Level II monitoring network in the UK

The effects of insect defoliators on throughfall and soil nutrient fluxes were studied in coniferous and deciduous stands at five UK intensive monitoring plots (1998 to 2008). Links were found between the dissolved organic carbon (DOC), nitrogen (N) and potassium (K) fluxes through the forest system to biological activity within the canopy. Underlying soil type determined the leaching or accumulation of these elements. Under oak, monitored at two sites, frass from caterpillars of Tortrix viridana and Operophtera brumata added direct deposition of ~ 16 kg ha⁻¹extra N during defoliation. Peaks of nitrate (NO₃-N) flux between 5 and 9 kg ha⁻¹ (×5 usual winter values) were recorded in consecutive years in shallow soil waters. Synchronous rises in deep soil NO₃-N fluxes at the Grizedale sandy site indicate downward flushing, not seen at the clay site. Under three Sitka spruce stands, generation of honeydew (DOC) was attributed to two aphid species (Elatobium abietinum and Cinara pilicornis) with distinctive feeding strategies. Throughfall DOC showed mean annual fluxes (6 seasons) ~ 45-60 kg ha⁻¹ compared with rainfall values of 14-22 kg ha⁻¹. Increases of total N in throughfall and NO₃-N fluxes in shallow soil solution were detected — soil water fluxes reached  8 kg ha⁻¹ in Llyn Brianne, ~ 25 kg ha⁻¹ in Tummel, and ~ 40 kg NO₃-N ha⁻¹ in Coalburn. At Tummel, on sandy soil, NO₃-N leaching showed increased concentration at depth, attributed to microbiological activity within the soil. By contrast, at Coalburn and Llyn Brianne, sites on peaty gleys, soil water NO₃-N was retained mostly within the humus layer. Soil type is thus key to predicting N movement and retention patterns. These long term analyses show important direct and indirect effects of phytophagous insects in forest ecosystems, on above and below ground processes affecting tree growth, soil condition, vegetation and water quality.     

Diesel vehicle emission and death rates in Tokyo, Japan: a natural experiment

Evidence linking air pollution with adverse cardiopulmonary outcomes is accumulating. However, few studies have been conducted to evaluate whether vehicle emission control improves public health. We thus evaluated the effect of a diesel emission control law on mortality rates in 23 wards of Tokyo metropolitan area, Japan. We obtained daily counts of mortality and concentrations of nitrogen dioxide (NO₂) and particulate matter less than 2.5 μm in diameter (PM_2.5) from April 2003 to December 2008. Time-series and interrupted time-series analysis were employed to analyze the data in two periods: prior to the introduction of tighter restrictions (April 2003 to March 2006) and after the enforcement (April 2006 to December 2008). Concentrations of air pollutants gradually decreased during the study period: from 36.3 ppb (NO₂) and 22.8 μg/m³ (PM_2.5) to 32.1 ppb and 20.3 μg/m³, respectively. Air pollutants were positively associated with circulatory and pulmonary disease mortality, especially cerebrovascular disease. Each same-day PM_2.5 increase of 10 μg/m³ was associated with a 1.3% increase in cerebrovascular mortality rate (95% confidence interval: 0.2-2.4). Rate ratios were attenuated after the enforcement in most of the outcomes, probably due to reduced toxicity of the pollutants. In the crude interrupted time-series analysis, reductions of standardized mortality rates after the enforcement were the greatest in high traffic areas. Even after adjustment of longer-time trend, mortality rate from cerebrovascular disease was reduced by 8.50% (p < .001) with dose-response relationship. However, the declines in other cause-specific mortality became equivocal. This natural experiment in Tokyo suggests that emission controls improved air quality. Although suggestive, further data are needed to conclusively demonstrate an impact on mortality rates.     

The association between fine particulate air pollution and hospital emergency room visits for cardiovascular diseases in Beijing, China

Background

Because epidemiological studies have yielded different results, the association between exposure to fine particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) and acute events of cardiovascular diseases (CVD) is unknown. Additionally, no research has been conducted to explore the association between PM_2.5 and hospital emergency room (ER) visits of cardiovascular diseases in Beijing, China.

Objective

To explore the association between PM_2.5 and the hospital ER visits in Beijing, China for CVD {(International Classification of Diseases, 10th vision (ICD-10): I00~I99)}.

Methods

We collected data for daily hospital ER visits for CVD from the Peking University Third Hospital, daily ambient PM_2.5 data from a fixed monitor site at Peking University, and data on the daily level of gaseous air pollutants {sulfur dioxide (SO₂) and nitrogen dioxide (NO₂)} from the Beijing Municipal Environmental Monitoring Center between June 1, 2004 and December 31, 2006. A time-stratified case-crossover design was used to evaluate associations between CVD health outcomes and ambient air pollutants.

Results

8377 hospital ER visits of CVD were collected in our study. After adjusting the temperature and the relative humidity, the associations for 10 μg/m³ increases in levels of PM_2.5, SO₂, or NO₂ and hospital ER visits for cardiovascular diseases were statistically significant with odds ratios (ORs) of 1.005{95% confidence interval (CI): 1.001-1.009}, 1.014(95% CI: 1.004-1.024), and 1.016(95% CI: 1.003-1.029), respectively.

Conclusion

These findings suggest that elevated levels of ambient air pollutants are associated with the increase in hospital ER visits for CVD in Beijing, China.     

Sources and timing of anthropogenic pollution in the Ensenada de San Simon (inner Ria de Vigo), Galicia, NW Spain: an application of mixture-modelling and nonlinear optimization to recent sedimentation

The Ensenada de San Simon is the inner part of the Ria de Vigo, one of the major mesotidal rias of the Galician coast, NW Spain. The geochemistry of its bottom sediments can be accounted for in terms of both natural and anthropogenic sources. Mixture-modelling enables much of the Cr, Ni, V, Cu, Pb and Zn concentrations of the bottom and subaqueous sediments to be explained by sediment input from the river systems and faecal matter from manmade mussel rafts. The compositions and relative contributions of additional, unknown, sources of anomalous heavy-metal concentrations are quantified using constrained nonlinear optimization. The pattern of metal enrichment is attributed to: material carried in solution and suspension in marine water entering the Ensenada from the polluted industrial areas of the adjacent Ria de Vigo; wind-borne urban dusts and/or vehicular emissions from the surrounding network of roads and a motorway road-bridge over the Estrecho de Rande; industrial and agricultural pollution from the R. Redondela; and waste from a former ceramics factory near the mouth of the combined R. Oitaben and R. Verdugo. Using (137)Cs dating, it is suggested that heavy metal build-up in the sediments since the late 1970s followed development of inshore fisheries and introduction of the mussel rafts (ca. 1960) and increasing industrialisation.     

Respiratory health, effects of ambient air pollution and its modification by air humidity in Drobeta-Turnu Severin, Romania

Background

Associations between ambient air pollution and respiratory health have been mainly reported for Western Europe and Northern America.

Objectives

Our goal was to investigate such associations among the population of Drobeta-Turnu Severin, Romania, a city in Central Eastern Europe (CEE), and to quantify their modification by air humidity. The latter is of increased interest for the current discussion about the potential effects of climate change on human health.

Methods

We investigated (study period: 23.01.2001-31.08.2002) the associations between chronic obstructive pulmonary disease (COPD), asthma and chronic bronchitis (CB) and total suspended particles (TSP), sulphur dioxide (SO₂) and nitrogen dioxide (NO₂). Generalized additive models (GAM) controlling for time patterns and weather effects were applied. Delayed effects up to seven days were analysed in single lag and polynomial distributed lag models (PDLMs).

Results

An increase of 10 µg/m³ TSP was related to a 3.3% (95% CI: 0.3%-6.4%) and a 2.8% (95% CI: 0.1%-5.7%) increase for hospital admissions for chronic bronchitis with a lag of one and four days, respectively. The adverse effect of TSP on chronic bronchitis was reduced by higher humidity. An increase of 10 µg/m³ SO₂ was related to a 6% (95% CI: 7%-25%) increase, with a two days lag, for hospital admissions for chronic bronchitis. We have not been able to identify a threshold, below which ambient TSP and SO₂ concentrations have no effect on hospital admissions for chronic bronchitis. We found adverse but nonsignificant influences of TSP, SO₂ and NO₂ on total respiratory hospital admissions, COPD and asthma and NO₂ on chronic bronchitis.

Conclusions

We conclude that in Drobeta-Turnu Severin CB is associated with TSP and mainly SO₂. Dry air aggravates the adverse effect of TSP.