Sulfur or Pollen? Chemical, Biological, and Toxicological Basis for the Correct Risk Communication of Urban Yellow Dust Deposition.

Urban yellow dust deposition is a common phenomenon in many parts of the world, which is sometimes called "sulfur shower," "sulfur rain," or "pollen storm." Most people, especially those living in the vicinity of industrial facilities, wrongly perceive the yellow dust as sulfur when in fact it is pollen. The misunderstanding increases risk perception as people believe the "yellow powder" is a serious threat to their health. Based on simple observations, it is virtually impossible to differentiate sulfur from pollen, so risk communication should consider the chemical, biological, and toxicological aspects of these agents. In this review, we clarify that industrial emissions of sulfur are under the form of sulfides, oxides, and other volatile compounds which are gaseous and noncolored, and we explain that it is chemically impossible for gaseous sulfur to become solid yellow sulfur under normal environmental conditions. We also describe pollen and its release from trees, shrubs, and herbs a process influenced by atmospheric conditions. We suggest take-home messages that risk communicators may use when explaining the phenomenon to their communities.

Functionalized carbon quantum dots as fluorescent nanoprobe for determination of tetracyclines and cell imaging.

Nitrogen and sulfur co-doped carbon dots (N, S-CQDs) with high fluorescent, water-soluble, low-toxicity properties were synthesized by microwave-assisted hydrothermal approach. The prepared N, S-CDs exhibited high selectivity in detection of tetracyclines (TCs) and displayed a fast-responsive fluorescence quenching signal in the mixture, which are mainly attributed to the inner filter effect (IFE). The synthesized N, S-CQDs are successfully used as a fluorescent nanoprobe for the determination of CTC in milk samples (with excitation/emission maxima at 373/424 nm). The limit of detection (LOD) is 71 ng mL-1, and the recoveries of spiked samples range from 96 to 104% with a relative standard deviations (RSDs) less than 2.7% (n = 3). Additionally, the cytotoxicity and optical imaging performance of N, S-CQDs were preliminarily evaluated. The results indicate the low-toxicity and good biocompatibility of the N, S-CQDs and their promising future as fluorescent-imaging agents in pharmaceutical analysis. Graphical Abstract Synthesis flowchart and application of nitrogen and sulfur dual-doped carbon quantum dots.

Nitrogen, phosphorus and sulfur tri-doped carbon dots are specific and sensitive fluorescent probes for determination of chromium(VI) in water samples and in living cells.

A rapid, sensitive, and selective fluorometric assay is described for the determination of chromium(VI) in real waters and living cells. The method is making use of nitrogen, phosphorus, and sulfur tri-doped carbon dots (NPS-CDs) which have absorption/emission maxima at 360/505 nm/nm. Cr(VI) has an absorption maximum at 350 nm and causes an inner filter effect (IFE) on the blue fluorescence of the NPS-CDs. The NPS-CDs were hydrothermally synthesized using p-aminobenzenesulfonic acid and tetrakis(hydroxymethyl)phosphonium chloride as precursors. The NPS-CDs were characterized by transmission electron microscopy, X-ray diffraction, and several spectroscopic methods. They are biocompatible and negligibly cytotoxic when tested with HeLa cells and MCF-7 cells even after 48 h of incubation. The NPS-CDs were used as fluorescent probes for Cr(VI). The detection limit is 0.23 µM (three times standard deviation versus slope), and the linear response covers the 1 to 500 µM chromate concentration range. The NPS-CDs were applied to the determination of Cr(VI) in real waters and living cells (HeLa and MCF-7) and gave satisfying results. Graphical abstractSchematic representation of hydrothermal synthesis of nitrogen, phosphorus, and sulfur tri-doped carbon dots (NPS-CDs) for Cr(VI) detection via inner filter effect (IFE). NPS-CDs were applied to the determination of Cr(VI) in living cells (HeLa and MCF-7) with satisfying results.

Phytotoxicity of polymetallic mine wastes from southern Tuscany and Saxony.

Restoration potential of mine wastes or approaches to improve soil conditions and to ameliorate phytotoxicity on these sites may be simulated in standardized greenhouse experiments. Plants can be cultivated side by side on materials from different origins in dilution series with defined admixtures of certain aggregates. Mine wastes used in the present study originated from Fenice Capanne (FC, Tuscany, Italy) and Altenberg (ALT, Saxony, Germany). Tailings of the Italian site contain high concentrations of lead, zinc, arsenic and sulphur while tin, wolfram, molybdenum and lithium are highly elevated in the German mine waste. We tested growth responses of five crop species and analyzed concentrations of various metals and nutrients in the shoot to evaluate the toxicity of the FC mine waste and found oilseed rape being the most and corn the least resistant crop. Interestingly, oilseed rape accumulated seven times higher levels of lead than corn without showing adverse effects on productivity. In a subsequent comparison of FC and ALT mine waste, we cultivated different species of buckwheat (Fagopyrum spec.), a fast growing genus that evolved in mountain areas and that has been shown to be tolerant to low pH and high concentrations of metals. We found that the FC mine waste was more toxic than the ALT substrate in F. tataricum and F. esculentum. However, lower admixtures of FC material (10%) resulted in stronger growth reductions than higher proportions (25%) of the mine waste which was primarily related to the slightly lower pH and higher availability of essential metals due to the admixture of sand. These results confirm the importance of managing the soil chemical and physical characteristics of wastelands and call for the development of assisted reclamation to prepare sites for regular biomass production.

The interactive effect of fungicide residues and yeast assimilable nitrogen on fermentation kinetics and hydrogen sulfide production during cider fermentation.

BACKGROUND: Fungicide residues on fruit may adversely affect yeast during cider fermentation, leading to sluggish or stuck fermentation or the production of hydrogen sulfide (H2 S), which is an undesirable aroma compound. This phenomenon has been studied in grape fermentation but not in apple fermentation. Low nitrogen availability, which is characteristic of apples, may further exacerbate the effects of fungicides on yeast during fermentation. The present study explored the effects of three fungicides: elemental sulfur (S0 ) (known to result in increased H2 S in wine); fenbuconazole (used in orchards but not vineyards); and fludioxonil (used in post-harvest storage of apples). RESULTS: Only S0 led to increased H2 S production. Fenbuconazole (≥0.2 mg L-1 ) resulted in a decreased fermentation rate and increased residual sugar. An interactive effect of yeast assimilable nitrogen (YAN) concentration and fenbuconazole was observed such that increasing the YAN concentration alleviated the negative effects of fenbuconazole on fermentation kinetics. CONCLUSION: Cidermakers should be aware that residual fenbuconazole (as low as 0.2 mg L-1 ) in apple juice may lead to stuck fermentation, especially when the YAN concentration is below 250 mg L-1 . These results indicate that fermentation problems attributed to low YAN may be caused or exacerbated by additional factors such as fungicide residues, which have a greater impact on fermentation performance under low YAN conditions. © 2016 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Antioxidant, photosynthesis and growth characteristics of plants grown in high sulphur coalmine overburden.

North East region of India suffers from high sulphur coal mine overburden (OB) and plants those survive under such condition have adopted to such harsh environment. Here, we have investigated the effect of coal mine OB substrate on biochemical, physiological and growth of two shrubs Cassia (Cassia sofera L.) and Dhaincha (Sesbania rostrata L.); two tree species Gomari (Gmelina arborea L.) and Sisso (Dalbergia sisso L.); and two monocots Citronella Grass (Cymbopogon winterianus Jowitt) and Lemon Grass (Cymbopogon citratus L). The mine OB was found to be acidic (pH 2.0) with no true soil behavior, 12.5% sulphur and more than double the trace and heavy metals compared to normal control soil. Overall, high lipid peroxidation, membrane damage, peroxidase, glutathione reductase, ascorbate peroxidase, superoxide dismutase enzymes activities along with osmolyte proline and total soluble sugar was found in mine OB plants compared to control plants. While antioxidant activities were higher, nitrate reductase activity was significantly low but reduced leaf area, total shoot and root biomass. However, the responses of antioxidant activities in mine OB plants and control plants did not follow a standard pattern of higher activities in roots followed by old>young leaves or vice versa. Further, in mine OB plants, lipid peroxidation was found significantly higher for young citronella leaves. The levels of higher glutathione reductase was found in roots than the leaves except for old leaves in Gomari while ascorbate peroxidase was found in the leaves than the roots. Overall, all the species showed higher antioxidant enzyme activities, osmolyte accumulation and membrane damage possibly due to acidity and significantly higher limit of trace and heavy metals in mine OB substrate.

Evidence of recovery of Juniperus virginiana trees from sulfur pollution after the Clean Air Act.

Using dendroisotopic techniques, we show the recovery of Juniperus virginiana L. (eastern red cedar) trees in the Central Appalachian Mountains from decades of acidic pollution. Acid deposition over much of the 20th century reduced stomatal conductance of leaves, thereby increasing intrinsic water-use efficiency of the Juniperus trees. These data indicate that the stomata of Juniperus may be more sensitive to acid deposition than to increasing atmospheric CO2. A breakpoint in the 100-y δ(13)C tree ring chronology occurred around 1980, as the legacy of sulfur dioxide emissions declined following the enactment of the Clean Air Act in 1970, indicating a gradual increase in stomatal conductance (despite rising levels of atmospheric CO2) and a concurrent increase in photosynthesis related to decreasing acid deposition and increasing atmospheric CO2. Tree ring δ(34)S shows a synchronous change in the sources of sulfur used at the whole-tree level that indicates a reduced anthropogenic influence. The increase in growth and the δ(13)C and δ(34)S trends in the tree ring chronology of these Juniperus trees provide evidence for a distinct physiological response to changes in atmospheric SO2 emissions since ∼1980 and signify the positive impacts of landmark environmental legislation to facilitate recovery of forest ecosystems from acid deposition.

Interaction between sulfur and lead in toxicity, iron plaque formation and lead accumulation in rice plant.

Human activities have resulted in lead and sulfur accumulation in paddy soils in parts of southern China. A combined soil-sand pot experiment was conducted to investigate the influence of S supply on iron plaque formation and Pb accumulation in rice (Oryza sativa L.) under two Pb levels (0 and 600 mg kg(-1)), combined with four S concentrations (0, 30, 60, and 120 mg kg(-1)). Results showed that S supply significantly decreased Pb accumulation in straw and grains of rice. This result may be attributed to the enhancement of Fe plaque formation, decrease of Pb availability in soil, and increase of reduced glutathione (GSH) in rice leaves. Moderate S supply (30 mg kg(-1)) significantly increased Fe plaque formation on the root surface and in the rhizosphere, whereas excessive S supply (60 and 120 mg kg(-1)) significantly decreased the amounts of iron plaque on the root surface. Sulfur supply significantly enhanced the GSH contents in leaves of rice plants under Pb treatment. With excessive S application, the rice root acted as a more effective barrier to Pb accumulation compared with iron plaque. Excessive S supply may result in a higher monosulfide toxicity and decreased iron plaque formation on the root surface during flooded conditions. However, excessive S supply could effectively decrease Pb availability in soils and reduce Pb accumulation in rice plants.

Ecology and application of haloalkaliphilic anaerobic microbial communities.

Haloalkaliphilic microorganisms that grow optimally at high-pH and high-salinity conditions can be found in natural environments such as soda lakes. These globally spread lakes harbour interesting anaerobic microorganisms that have the potential of being applied in existing technologies or create new opportunities. In this review, we discuss the potential application of haloalkaliphilic anaerobic microbial communities in the fermentation of lignocellulosic feedstocks material subjected to an alkaline pre-treatment, methane production and sulfur removal technology. Also, the general advantages of operation at haloalkaline conditions, such as low volatile fatty acid and sulfide toxicity, are addressed. Finally, an outlook into the main challenges like ammonia toxicity and lack of aggregation is provided.

Photoinactivation of Escherichia coli by sulfur-doped and nitrogen-fluorine-codoped TiO2 nanoparticles under solar simulated light and visible light irradiation.

Titanium dioxide (TiO2) is one of the most widely used photocatalysts for the degradation of organic contaminants in water and air. Visible light (VL) activated sulfur-doped TiO2 (S-TiO2) and nitrogen-fluorine-codoped TiO2 (N-F-TiO2) were synthesized by sol-gel methods and characterized. Their photoinactivation performance was tested against Escherichia coli under solar simulated light (SSL) and VL irradiation with comparison to commercially available TiO2. Undoped Degussa-Evonik P-25 (P-25) and Sigma-TiO2 showed the highest photocatalytic activity toward E. coli inactivation under SSL irradiation, while S-TiO2 showed a moderate toxicity. After VL irradiation, Sigma-TiO2 showed higher photoinactivation, whereas S-TiO2 and P-25 showed moderate toxicity. Oxidative stress to E. coli occurred via formation of hydroxyl radicals leading to lipid peroxidation as the primary mechanism of bacterial inactivation. Various other biological models, including human keratinocytes (HaCaT), zebrafish liver cells (ZFL), and zebrafish embryos were also used to study the toxicity of TiO2 NPs. In conclusion, N-F-TiO2 did not show any toxicity based on the assay results from all the biological models used in this study, whereas S-TiO2 was toxic to zebrafish embryos under all the test conditions. These findings also demonstrate that the tested TiO2 nanoparticles do not show any adverse effects in HaCaT and ZFL cells.

Investigation of antimicrobial physiology of orthorhombic and monoclinic nanoallotropes of sulfur at the interface of transcriptome and metabolome.

Nanosized elemental sulfur (ES) is already reported to exert superior antimicrobial efficacy than micron-sized ES, which encourages their use in drugs and therapeutics. The aim of the present study is to explore the possible route and mode of antimicrobial action of orthorhombic (α-SNPs) and monoclinic (ß-SNPs) allotropes of sulfur, respectively, at their nano-dimensions. The antimicrobial efficacy of α- and ß-SNPs was determined against both the conventionally ES-resistant and ES-susceptible fungi and bacteria. Both the SNPs inhibited the microbial growth, irrespective of their resistance profile to ES and caused significant deformities on the microbial cell surfaces. However, the extent of antimicrobial efficacy was found to be optimum for α-SNPs, which can be attributed to their size, shape, and surface modification. Subsequent transcript profiling, metabolite profiling, and enzymatic analyses revealed that α- and ß-SNPs impaired a cluster of mitochondrial enzymes involved in cellular respiration and oxidative phosphorylation. ES and SNPs stress were found to elicit the NADPH-dependent glutathione reductase mediated ES-detoxification response in fungi and caused them to undertake the glyoxylate shunt in favor of energy conservation. A simultaneous study was also undertaken to assess the biocompatible or bio-adverse properties of SNPs in terms of their cytotoxic and genotoxic effects against the human derived lung fibroblast cell line (MRC-5). The present study hence explores the antimicrobial physiology of two novel functional materials and demonstrates their compatibility as a future putative antimicrobial drug.

Effects of high-sulphur water on hepatic gene expression of steers fed fibre-based diets.

Sulphur-induced polioencephalomalacia (sPEM), a neurological disorder affecting ruminants, is frequently associated with the consumption of high-sulphur (S) water and subsequent poor performance. Currently, there is no economical method for S removal from surface water sources, and alternative water sources are typically neither readily available nor cost-effective. Determination of genes differentially expressed in response to high-S water consumption may provide a better understanding of the physiology corresponding to high dietary S and ultimately lead to the development of treatment and prevention strategies. The objective of this study was to determine changes in gene expression in the liver, an organ important for S metabolism, of fibre-fed steers consuming high-S water. For this study, liver tissues were collected on the final day of a trial from yearling steers randomly assigned to low-S water control (566 mg/kg SO4 ; n = 24), high-S water (3651 mg/kg SO4 ; n = 24) or high-S water plus clinoptilolite supplemented at either 2.5% (n = 24) or 5.0% (n = 24) of diet dry matter (DM). Microarray analyses on randomly selected healthy low-S control (n = 4) and high-S (n = 4; no clinoptilolite) steers using the Affymetrix GeneChip Bovine Genome Array revealed 488 genes upregulated (p < 0.05) and 154 genes downregulated (p < 0.05) in response to the high- vs. low-S water consumption. Real-time RT-PCR confirmed the upregulation (p < 0.10) of seven genes involved in inflammatory response and immune functions. Changes in such genes suggest that ruminant animals administered high-S water may be undergoing an inflammation or immune response, even if signs of sPEM or compromised health are not readily observed. Further study of these, and other affected genes, may deliver new insights into the physiology underlying the response to high dietary S, ultimately leading to the development of treatments for high S-affected ruminant livestock.

The etymological role of the main atmosphere pollutants in development of human diseases.

The aim of research was monitoring of the main atmospheric air pollutants concentration on Adjara Autonomous Republic territory in order to determine their role in causing different diseases. The following atmospheric air pollutants have been determined in Batumi: dust, carbon monoxide, sulfur and nitrogen dioxide. The number of diseases registered in Adjara Autonomous Republic, which may be linked to the air pollution, has been studied. These are the following: chronic and nonspecific bronchitis, asthma and asthma status diseases, allergic rhinitis, trachea-, bronchi- and lung malignant tumor. In order to reduce the number of risk-factors significant attention should be paid to the proper functionality of the vehicles and systematic observations should continue on the chemical pollution of the air to make proper decisions to reduce the number of diseases.

Exploring the nephrotoxicity of sulfur-containing derivatives in sulfur-fumigated Panacis Quinquefolii Radix based on chemical profiling and untargeted metabolomics.

ETHNOPHARMACOLOGICAL RELEVANCE: Panacis Quinquefolii Radix (PQR) is often illegally sulfur fumigated to extend shelf life and improve appearance, but existing regulations of detecting SO2 residues do not accurately identify desulfurized sulfur-fumigated PQR (SF-PQR). Although sulfur-containing derivatives (SCDs) have been reported in some sulfur-fumigated herbs, there is a lack of research on the generation mechanisms and toxicity of SCDs. Our previous study reported the nephrotoxicity of SF-PQR, and there is an urgent necessity to illuminate the mechanism of toxicity as well as its association with SCDs. AIM OF THE STUDY: To investigate the transformation pattern of chemical components and SCDs in SF-PQR, and to disclose the linkage between SCDs and SF-PQR nephrotoxicity. MATERIALS AND METHODS: The extracts of PQR (before and after SF) were detected by the UPLC-LTQ-Orbitrap-MS method, and SCDs were screened as quality markers (Q-markers). The composition of sulfur combustion products was examined by ion chromatography to exploit the conversion mechanism of SCDs. After administration of PQR extracts to mice for two weeks, serum was collected for GC-MS-based untargeted metabolomics study to mine for differential metabolites. The upstream genes were traced by network analysis to probe toxicity targets. Molecular docking was used to uncover the interactions between SCDs and the targets. RESULTS: Thirty-three compounds were identified and 11 SCDs of saponins were screened, including four SO3 sulfonation products and five H2SO3 sulfonation products. Metabolomics study showed significant alterations in serum biochemistry of SF-PQR group, with substantial increases in fumarate and 2-heptanone content, and induced disturbances in glycerolipid metabolism and phenylalanine, tyrosine, and tryptophan biosynthesis in mice. Network analysis revealed that the key toxicity targets were DECR1, PLA2G1B, and CAT. Molecular docking indicated that SCDs had stable interaction forces with the above three toxicity targets. CONCLUSION: SF-PQR caused kidney damage by affecting glycerolipid metabolism and phenylalanine, tyrosine, and tryptophan biosynthesis. Eleven SCDs were potential nephrotoxic substances and Q-markers for identifying SF-PQR. This study is the first to systematically elucidate the mechanism of SF-PQR-related nephrotoxicity, providing a robust basis for the construction of new quality control standards and a global prohibition of sulfur fumigation.

Transcriptional response of Medicago truncatula sulphate transporters to arbuscular mycorrhizal symbiosis with and without sulphur stress.

Sulphur is an essential macronutrient for plant growth, development and response to various abiotic and biotic stresses due to its key role in the biosynthesis of many S-containing compounds. Sulphate represents a very small portion of soil S pull and it is the only form that plant roots can uptake and mobilize through H(+)-dependent co-transport processes implying sulphate transporters. Unlike the other organically bound forms of S, sulphate is normally leached from soils due to its solubility in water, thus reducing its availability to plants. Although our knowledge of plant sulphate transporters has been growing significantly in the past decades, little is still known about the effect of the arbuscular mycorrhiza interaction on sulphur uptake. Carbon, nitrogen and sulphur measurements in plant parts and expression analysis of genes encoding putative Medicago sulphate transporters (MtSULTRs) were performed to better understand the beneficial effects of mycorrhizal interaction on Medicago truncatula plants colonized by Glomus intraradices at different sulphate concentrations. Mycorrhization significantly promoted plant growth and sulphur content, suggesting increased sulphate absorption. In silico analyses allowed identifying eight putative MtSULTRs phylogenetically distributed over the four sulphate transporter groups. Some putative MtSULTRs were transcribed differentially in roots and leaves and affected by sulphate concentration, while others were more constitutively transcribed. Mycorrhizal-inducible and -repressed MtSULTRs transcripts were identified allowing to shed light on the role of mycorrhizal interaction in sulphate uptake.

Polyethylene glycol-stabilized sulphur nanoparticles: an effective antimicrobial agent against multidrug-resistant bacteria.

OBJECTIVES: To elucidate the antibacterial efficacy of chemically synthesized and custom-made sulphur nanoparticles (SNPs) of two different sizes and surface modifications against a number of multidrug-resistant Gram-negative bacilli (GNB) harbouring the New Delhi metallo-ß-lactamase 1 enzyme (NDM-1). METHODS: Antimicrobial susceptibility of the isolates was determined. The strains were evaluated for the presence of carbapenemases, ß-lactamases, 16S rRNA methylases and integrons. Chemically synthesized, polyethylene-glycol (PEG)-stabilized SNPs of 10 nm and custom-made non-capped SNPs of 60 nm were physicochemically characterized and evaluated for their antibacterial efficacy against multidrug-resistant GNB using the agar dilution method (ADM) and the broth microdilution method (BMD). The cytotoxicity of the chemically synthesized SNPs was evaluated with a human-derived hepatoma (HepG2) cell line using a WST-1 assay kit. RESULTS: All isolates were multidrug-resistant and possessed NDM-1 along with other ß-lactamases, 16S rRNA methylases and integron 1. Chemically synthesized PEGylated SNPs showed a bactericidal effect against all tested strains at a concentration between 9.41 and 18.82 mg/L using BMD. The ADM data revealed that SNPs had uniform MICs (18.82 mg/L) for all tested strains. On the other hand, custom-made SNPs failed to impart any antibacterial effect at the equivalent concentrations of chemically synthesized SNPs. The WST-1 assay revealed no significant cytotoxicity of the PEGylated SNPs even at the highest concentration (94.08 mg/L). CONCLUSIONS: To the best of our knowledge, this is the first attempted study to show the effectiveness of nanoparticles against multidrug-resistant GNB harbouring NDM-1.

Toxicity and elemental composition of particulate matter from outdoor and indoor air of elementary schools in Munich, Germany.

UNLABELLED: Outdoor particulate matter (PM(10)) is associated with detrimental health effects. However, individual PM(10) exposure occurs mostly indoors. We therefore compared the toxic effects of classroom, outdoor, and residential PM(10). Indoor and outdoor PM(10) was collected from six schools in Munich during teaching hours and in six homes. Particles were analyzed by scanning electron microscopy and X-ray spectroscopy (EDX). Toxicity was evaluated in human primary keratinocytes, lung epithelial cells and after metabolic activation by several human cytochromes P450. We found that PM(10) concentrations during teaching hours were 5.6-times higher than outdoors (117 ± 48 µg/m(3) vs. 21 ± 15 µg/m(3), P < 0.001). Compared to outdoors, indoor PM contained more silicate (36% of particle number), organic (29%, probably originating from human skin), and Ca-carbonate particles (12%, probably originating from paper). Outdoor PM contained more Ca-sulfate particles (38%). Indoor PM at 6 µg/cm(2) (10 µg/ml) caused toxicity in keratinocytes and in cells expressing CYP2B6 and CYP3A4. Toxicity by CYP2B6 was abolished with the reactive oxygen species scavenger N-acetylcysteine. We concluded that outdoor PM(10) and indoor PM(10) from homes were devoid of toxicity. Indoor PM(10) was elevated, chemically different and toxicologically more active than outdoor PM(10). Whether the effects translate into a significant health risk needs to be determined. Until then, we suggest better ventilation as a sensible option. PRACTICAL IMPLICATIONS: Indoor air PM(10) on an equal weight base is toxicologically more active than outdoor PM(10). In addition, indoor PM(10) concentrations are about six times higher than outdoor air. Thus, ventilation of classrooms with outdoor air will improve air quality and is likely to provide a health benefit. It is also easier than cleaning PM(10) from indoor air, which has proven to be tedious.

Impact of the 1990 Hong Kong legislation for restriction on sulfur content in fuel.

INTRODUCTION: After the implementation of a regulation restricting sulfur to 0.5% by weight in fuel on July 1, 1990, in Hong Kong, sulfur dioxide (SO2*) levels fell by 45% on average and as much as 80% in the most polluted districts (Hedley et al. 2002). In addition, a reduction of respiratory symptoms and an improvement in bronchial hyperresponsiveness in children were observed (Peters et al. 1996; Wong et al. 1998). A recent time-series study (Hedley et al. 2002) found an immediate reduction in mortality during the cool season at six months after the intervention, followed by an increase in cool-season mortality in the second and third years, suggesting that the reduction in pollution was associated with a delay in mortality. Proportional changes in mortality trends between the 5-year periods before and after the intervention were measured as relative risks and used to assess gains in life expectancy using the life table method (Hedley et al. 2002). To further explore the relation between changes in pollution-related mortality before and after the intervention, our study had three objectives: (1) to evaluate the short-term effects on mortality of changes in the pollutant mix after the Hong Kong sulfur intervention, particularly with changes in the particulate matter (PM) chemical species; (2) to improve the methodology for assessment of the health impact in terms of changes in life expectancy using linear regression models; and (3) to develop an approach for analyzing changes in life expectancy from Poisson regression models. A fourth overarching objective was to determine the relation between short- and long-term benefits due to an improvement in air quality. METHODS: For an assessment of the short-term effects on mortality due to changes in the pollutant mix, we developed Poisson regression Core Models with natural spline smoothers to control for long-term and seasonal confounding variations in the mortality counts and with covariates to adjust for temperature (T) and relative humidity (RH). We assessed the adequacy of the Core Models by evaluating the results against the Akaike Information Criterion, which stipulates that, at a minimum, partial autocorrelation plots should be between -0.1 and 0.1, and by examining the residual plots to make sure they were free from patterns. We assessed the effects for gaseous pollutants (NO2, SO2, and O3), PM with an aerodynamic diameter < or = 10 microm (PM10), and its chemical species (aluminum [Al], iron [Fe], manganese [Mn], nickel [Ni], vanadium [V], lead [Pb], and zinc [Zn]) using the Core Models, which were developed for the periods 5 years (or 2 years in the case of the sensitivity analysis) before and 5 years after the intervention, as well as in the10-year (or 7-year in the case of the sensitivity analysis) period pre- and post-intervention. We also included an indicator to separate the pre- and post-intervention periods, as well as the product of the indicator with an air pollution concentration variable. The health outcomes were mortality for all natural causes and for cardiovascular and respiratory causes, at all ages and in the 65 years or older age group. To assess the short- and long-term effects, we developed two methods: one using linear regression models reflecting the age-standardized mortality rate D(j) at day j, divided by a reference D(ref); and the other using Poisson regression models with daily mortality counts as the outcome variables. We also used both models to evaluate the relation between outcome variables and daily air pollution concentrations in the current day up to all previous days in the past 3 to 4 years. In the linear regression approach, we adjusted the data for temperature and relative humidity. We then removed season as a potential confounder, or deseasonalized them, by calculating a standard seasonal mortality rate profile, normalized to an annual average of unity, and dividing the mortality rates by this profile. Finally, to correct for long-term trends, we calculated a reference mortality rate D(ref)(j) as a moving average of the corrected and deseasonalized D(j) over the observation window. Then we regressed the outcome variable D(j)/D(ref) on an entire exposure sequence {c(i)} with lags up to 4 years in order to obtain impact coefficient f(i) from the regression model shown below: deltaD(j)/D (ref) = i(max)sigma f(i) c(j - i)(i = 0). The change in life expectancy (LE) for a change of units (deltac) in the concentration of pollutants on T(day)--representing the short interval (i.e., a day)--was calculated from the following equation (deltaL(pop) = average loss in life expectancy of an entire population): deltaL(pop) = -deltac T(day) infinity sigma (j = 0) infinity sigma f(i) (i = 0). In the Poisson regression approach, we fitted a distributed-lag model for exposure to previous days of up to 4 years in order to obtain the cumulative lag effect sigma beta(i). We fit the linear regression model of log(LE*/LE) = gamma(SMR - 1) + alpha to estimate the parameter gamma by gamma, where LE* and LE are life expectancy for an exposed and an unexposed population, respectively, and SMR represents the standardized mortality ratio. The life expectancy change per Ac increase in concentration is LE {exp[gamma delta c(sigma beta(i))]-1}. RESULTS: In our assessment of the changes in pollutant levels, the mean levels of SO2, Ni, and V showed a statistically significant decline, particularly in industrial areas. Ni and V showed the greatest impact on mortality, especially for respiratory diseases in the 5-year pre-intervention period for both the all-ages and 65+ groups among all chemical species. There were decreases in excess risks associated with Ni and V after the intervention, but they were nonsignificant. Using the linear regression approach, with a window of 1095 days (3 years), the losses in life expectancy with a 10-microg/m3 increase in concentrations, using two methods of estimation (one with adjustment for temperature and RH before the regression against pollutants, the other with adjustment for temperature and RH within the regression against pollutants), were 19.2 days (95% CI, 12.5 to 25.9) and 31.4 days (95% CI, 25.6 to 37.2) for PM10; and 19.7 days (95% CI, 15.2 to 24.2) and 12.8 days (95% CI, 8.9 to 16.8) for SO2. The losses in life expectancy in the current study were smaller than the ones implied by Elliott and colleagues (2007) and Pope and colleagues (2002) as expected since the observation window in our study was only 3 years whereas these other studies had windows of 16 years. In particular, the coefficients used by Elliott and colleagues (2007) for windows of 12 and 16 years were non-zero, which suggests that our window of at most 3 years cannot capture the full life expectancy loss and the effects were most likely underestimated. Using the Poisson regression approach, with a window of 1461 days (4 years), we found that a 10-microg/m3 increase in concentration of PM10 was associated with a change in life expectancy of -69 days (95% CI, -140 to 1) and a change of -133 days (95% CI, -172 to -94) for the same increase in SO2. The effect estimates varied as expected according to most variations in the sensitivity analysis model, specifically in terms of the Core Model definition, exposure windows, constraint of the lag effect pattern, and adjustment for smoking prevalence or socioeconomic status. CONCLUSIONS: Our results on the excess risks of mortality showed exposure to chemical species to be a health hazard. However, the statistical power was not sufficient to detect the differences between the pre- and post-intervention periods in Hong Kong due to the data limitations (specifically, the chemical species data were available only once every 6 days, and data were not available from some monitoring stations). Further work is needed to develop methods for maximizing the information from the data in order to assess any changes in effects due to the intervention. With complete daily air pollution and mortality data over a long period, time-series analysis methods can be applied to assess the short- and long-term effects of air pollution, in terms of changes in life expectancy. Further work is warranted to assess the duration and pattern of the health effects from an air pollution pulse (i.e., an episode of a rapid rise in air pollution) so as to determine an appropriate length and constraint on the distributed-lag assessment model.