The concentrations and particle size relationships of selected trace elements in fly ashes from U.K. coal-fired power plants and a refuse incinerator

Fly ash samples from 11 coal-fired power plants and a refuse incinerator in the U.K. were analyzed for total arsenic, cadmium, lead and selenium. Enrichment factor (EF) values calculated with respect to crustal abundance (EF_crust) were highest for cadmium and lead in refuse fly ash, with EFs of 2500 and 740, respectively. Enrichment factors for selenium were similar in both fly ash types; only arsenic was more enriched in coal fly ash compared with refuse fly ash. Despite the high EF_crust values of certain elements in the two fly ash types, the same elements showed EF values of about unity when expressed with respect to the starting material. Both materials displayed an inverse relationship between particle size and extent of enrichment for all the elements studied, but the degree of enrichment on the finest particles was lower than reported for coal fly ash by other workers. The EF_crust values estimated for arsenic, lead and selenium in suspended particulates from a refuse incinerator were similar to those calculated for the urban atmospheric aerosol, whereas cadmium was 10 times more enriched in the suspended particulates.Scanning electron microscopy revealed a marked contrast in the morphological features of the two fly ash types. Coal fly ash was almost entirely composed of cenospheres of < 20 μm diameter, whereas refuse fly ash consisted mostly of amorphous particles of < 50 μm diameter; some cenospheres were, however, noted in the refuse fly ash.     

Polynuclear aromatic hydrocarbon content of particulate matter suspended in the atmosphere of La Plata, Argentina

Twelve polynuclear aromatic hydrocarbons (PAH) were evaluated by chromatographic procedures using a HPLC-UV detector and a GC-FID detector. The PAH were evaluated in airborne particulate matter collected in La Plata, Argentina, over a period of 2 years (with sampling periods of approximately 4 months). The samples were size fractionated, and the PAH in each fraction determined. The analytical procedure used was as follows: extraction in benzene, concentration at room temperature, clean-up in a silica gel column and, finally, evaluation by chromatographic procedures. The extraction recovery was 76.2 +/- 5.8% for naphthalene and 96.0 +/- 6.2% for chrysene. Clean-up recovery was 87.8 +/- 7.15% for phenanthrene and 98.1 +/- 8.3% for anthracene. The largest PAH load was present in the smallest fractions. The smallest particles were carbonaceous in nature. The concentration peak was associated both with the total mass of airborne particulate matter and the reduction in amounts of coarse particles. The PAH distribution could not be correlated with characteristic physicochemical properties such as water solubility or the octanol-water distribution coefficient. The PAH load was greater in fall and winter than in spring and summer. This could be attributed to the reduction of photochemical processes during the cold seasons.     

Retrospective trend analysis of the content of U.K. air particulate material 1957–1974

Particulate air samples have been collected on a daily basis in a high volume air sampler at Chilton (Oxfordshire U.K.) a semi-rural site in southern England from 1957 to 1974. Although the samples collected on esparto grass filters were intended to measure debris from nuclear weapons, they have proved susceptible to analysis for a variety of inorganic elements and ions.The concentration of twenty-seven elements and ions have been determined by instrumental neutron activation analysis and other methods. Measurements were performed on three-monthly groups of samples over seventeen years. Comparison with another series of current measurements over the latter part of the period indicate that the results are probably valid and thus, may represent the longest period for which continuous data of this nature are available. The detailed results are presented here.There are marked fluctuations in the levels displayed which can be categorised in three ways.There are seasonal changes. Winter levels, due either to increased emission rates or to meteorological phenomena, are greater than summer. The largest seasonal differences occur with chalcophilic (volatile) elements.Medium term fluctuations, in which excursions continue over extended periods, occur in similar ways with most constituents. A difference between the behaviour of anthropogenic and marine components indicate a meteorological mechanism for these changes. The most interesting changes are those showing long term trends. Many elements exhibit initial high levels with a rapid decline to 1961 and thereafter fall more slowly. The similarity of this behaviour with that of local “black smoke” indicates a component in the inorganic aerosol at Chilton from coal burning or industrial sources. The behavior of some lithophilic elements suggests an additional natural source.The behaviour of lead is consistent with a rise in emissions from petrol although there appears to be a residual component from other anthropogenic sources. A rise in bromine levels too, might be similarly explained.Vanadium appears to arise from the combustion of fuel oil now in increasing use.Concentrations of ammonium sulphate rise during the summers of the survey. It is likely that a photochemical mechanism for the production of sulphur dioxide oxidants from automobile exhaust is responsible. Similar photochemical processes and other reactions may cause the rises of ammonium nitrate although these display less seasonal bias.This survey at a single site demonstrates the value of data gathered over a long period, and emphasises the need to conduct controlled measurements for similar times at a variety of differing environmental and geographical locations.     

The distribution of mercury, cadmium and lead between water and suspended matter in the Loire Estuary as a function of the hydrological regime

We examined Hg, Pb, Cd in filtered water and suspended sediments from the Loire Estuary. The metal concentration in both varies widely and is a function of hydrodynamic and hydraulic parameters. We classified them according to geographical repartition, salinity, tidal state etc. A laboratory study, monitored under the same conditions of salinity, showed the affinity of suspended material for Hg, Pb and Cd. The results of the two studies, in vivo and in vitro emphasize the importance of salinity in the metal repartition between water and sediments.     

Retrieval of suspended particulate matter concentrations in the Danube River from Landsat ETM data

Alternations in river channel morphology result in a disturbed natural transport of suspended particulate matter (SPM). Suspended particulate matter serves as a transport medium for various pollutants, e.g. heavy metals. It is therefore important to understand how artificial obstructions alter the natural transport of suspended matter. Measurements of SPM in rivers are traditionally carried out during in situ sampling campaigns, which can provide only a limited view of the actual spatial distribution of suspended matter over large distances. Several authors have studied how space-borne remote sensing could be used for mapping of water quality in standing waters, but with only little attention paid to rivers. This paper describes the methodology how a Landsat ETM image was used to map the spatial patterns of SPM in the Slovak portion of the Danube River. Results of our investigation reveal that the Danube River in Slovakia exhibits gradual longitudinal decrease in concentrations of SPM. Based on a strong relationship between the Landsat near-infrared band (TM4) and field measurements, we developed a map of suspended particulate matter in the Danube River with a standard error (SE) of 2.92 mg/L. This study aims to show how archived satellite data and historical water quality data can be used for monitoring of SPM in large rivers. A methodology describing the minimum samples required for sufficiently accurate results is discussed in this paper also.     

许氏平鮋消化管上皮细胞及消化腺组织学和组织化学

对许氏平Sebastesschlegeli(Hilgendorf)消化管中的上皮细胞及消化腺进行了组织学及组织化学的研究。经光学显微镜和扫描电镜观察,口咽腔、舌和食道黏膜表面为复层扁平细胞,含有杯状细胞和味蕾,上皮细胞表面具微脊(微皱襞)。食道下段复层扁平细胞中夹有单层柱状细胞。胃黏膜表面为单层柱状细胞,细胞表面具顶板。胃贲门和盲囊部有丰富胃腺,盲囊底部和幽门部无胃腺。肠黏膜表面为单层柱状细胞,小肠段杯状细胞丰富,幽门盲囊上皮细胞结构同小肠。另外,还研究了肝脏、胰腺和胆囊的结构。     

Lipid composition of suspended particulate matter (SPM) in a southeastern blackwater stream

Suspended particulate matter (SPM) was collected seasonally for 1 yr at third- and fifth-order sites in a blackwater stream on the coastal plain in South Carolina. Fatty acids with carbon chain lengths from C(12)-C(32) were the most abundant component among the lipid classes examined with total concentrations varying from 8.5 to 60.2 microgL(-1). Unsaturated fatty acids predominated while significant concentrations of the even-chained saturated components C(24)-C(30) derived from cuticular plant waxes were also found. Concentrations of aliphatic alcohols, with carbon chain lengths between C(16) and C(30), ranged from 0.52 to 2.73 microgL(-1) and was dominated by the higher molecular weight compounds (C(22)-C(30)) derived primarily from cuticular plant waxes. Total hydrocarbon concentrations ranged from 0.35 to 5.66 microgL(-1) and showed no discernible trends with time or consistent difference between sites. The hydrocarbon assemblage observed indicates that these components are entirely of biogenic origin with no detectable anthropogenic contribution.The ratios of unsaturated to saturated fatty acids and cuticular to noncuticular fatty acids and alcohols at both stream locations indicate that the organic detritus associated with SPM collected during November and January is of more recent origin and less processed than that collected in the spring and summer months. Lipid concentrations at the third-order site generally had higher and more variable concentrations of the lipid classes compared with the fifth-order site. The ratio of saturated to unsaturated fatty acids was higher at the third-order site indicating that the organic fraction of SPM at this site was of more recent origin and less decomposed. The ratios of cuticular to noncuticular fatty acids and alcohols support this conclusion. These results indicate an export of particulate lipids of higher carbon resource quality from upstream to lower stream reaches.     

Natural, anthropogenic and fossil organic matter in river sediments and suspended particulate matter: a multi-molecular marker approach

Different classes of organic matter (OM) have been systematically investigated in sediments and suspended particulate matter (SPM) along the Danube River in order to understand causes of compositional changes. Analytical pyrolysis revealed the dominance of natural organic matter (NOM) in most of the samples. The predominance of aquatic biomass is evident mainly from the abundance of organonitrogen compounds and phenol distributions. As the river enters a forested gorge, the terrestrial component of the NOM in sediments is more significant. This is reflected in abundant methoxyphenols and a very high carbon preference index. SPM sample from a tributary shows a unique geochemical signature. It contains abundant carboxylic acids, amines, isoprenoids in the pyrolyzate, and is dominated by phytol and 24-methyl-cholesta-5,24(28)-dien-3β-ol in the extract, produced by a diatom bloom. Wax esters with a relatively high proportion of short, methyl-branched alkyl-chains appear together with abundant phytadienes and n-C₁₇ alkane in some samples, suggesting a microbial origin. Anthropogenic OM from runoff and atmospheric deposition was evident from a minor input of polycyclic aromatic hydrocarbons (PAHs) originating from mixed combustion sources. Multivariate analysis using PAH data led us to define simple molecular ratios to distinguish the PAH composition in sand and silty sediments. The newly defined ratios are the alkylated phenanthrenes and anthracenes ratio (APA; C₁-C₃/C₀-C₃ phenanthrenes and anthracenes) and the PAH ring number ratio (RN; 5-6 ring parent PAHs/all parent PAHs). This demonstrates that alkylated, as well as 5-6 ring PAHs are better preserved in the finer than in coarser grained sediments. A ubiquitous, but minor input of petroleum-related contamination with a uniform composition was evident in all samples as revealed by the analysis of petroleum biomarkers. This study demonstrates that the investigation of different classes of riverine OM requires a detailed molecular analysis, applying a series of analytical techniques and adequate statistical data treatment.     

Solid state partitioning of trace metals in suspended particulate matter from a river system affected by smelting-waste drainage

The partitioning of particulate trace metals was investigated during one year of monthly sampling of suspended particulate matter (SPM) at eight sites along the Lot-Garonne fluvial system, known for its polymetallic pollution. The chemical partitioning in five operationally defined fractions (exchangeable/carbonate, Fe/Mn oxides, organic matter/sulfides, acid soluble, residual) was determined using a multiple single extraction approach. This approach showed that Cd, Zn, Pb and Cu were mainly associated with acid soluble phases (84-95%, 65-88%, 61-82% and 55-80% of the respective total metal content), and therefore showed a high mean potential of mobilization and bioavailability. In the Riou-Mort River, draining the smelting-wastes, Zn, Cd and Mn showed high mobility as they were little associated with the residual fraction (1-2%) and mainly bound to the 'exchangeable' fraction of SPM (60-80%), probably weakly adsorbed on amorphous freshly-precipitated sulfide and/or oxide phases. Upstream and downstream of the anthropogenic source of metallic pollution, Mn and Cd, and Zn to a lesser extent, remained highly reactive. The other trace metals were mainly associated with the residual fraction and thus less mobile. However, the multiple single extraction scheme revealed that the most reactive transport phases were non-selectively extracted by the conventional extractants used here. These selectivity problems could not have been observed if sequential extraction was used.     

Heavy metal content of oysters from the Lynher Estuary,U.K.

The concentrations of As, Cd, Cu, Hg, Pb and Zn have been determined in oysters and sediments from the Lynher Estuary, U.K. The sediments contained high levels of Cu, Fe, Pb and Zn probably associated with run off from a metalliferous catchment area and high Hg associated with a local sewage input. In contrast, the analyses of the oyster tissue showed that only Cu and Zn were concentrated in the flesh. The majority of samples contained coliform bacteria in excess of 1000 organisms per ml of tissue. It is concluded that the quality of the oysters from this fishery was limited by the bacteriological cleanliness rather than toxic metal content.     

The influence of contrasting suspended particulate matter transport regimes on the bias and precision of flux estimates

A large database (507 station-years) of daily suspended particulate matter (SPM) concentration and discharge data from 36 stations on river basins ranging from 600 km(2) to 600,000 km(2) in size (USA and Europe) was collected to assess the effects of SPM transport regime on bias and imprecision of flux estimates when using infrequent surveys and the discharge-weighted mean concentration method. By extracting individual SPM concentrations and corresponding discharge values from the database, sampling frequencies from 12 to 200 per year were simulated using Monte Carlo techniques. The resulting estimates of yearly SPM fluxes were compared to reference fluxes derived from the complete database. For each station and given frequency, bias was measured by the median of relative errors between estimated and reference fluxes, and imprecision by the difference between the upper and lower deciles of relative errors. Results show that the SPM transport regime of rivers affects the bias and imprecision of fluxes estimated by the discharge-weighted mean concentration method for given sampling frequencies (e.g. weekly, bimonthly, monthly). The percentage of annual SPM flux discharged in 2% of time (Ms(2)) is a robust indicator of SPM transport regime directly related to bias and imprecision. These errors are linked to the Ms(2) indicator for various sampling frequencies within a specific nomograph. For instance, based on a deviation of simulated flux estimates from reference fluxes lower than +/-20% and a bias lower than 1% or 2%, the required sampling intervals are less than 3 days for rivers with Ms(2) greater than 40% (basin size<10,000 km(2)), between 3 and 5 days for rivers with Ms(2) between 30 and 40% (basin size between 10,000 and 50,000 km(2)), between 5 and 12 days for Ms(2) from 20% to 30% (basin size between 50,000 and 200,000 km(2)), 12-20 days for Ms(2) in the 15-20% range (basin size between 200,000 and 500,000 km(2)).     

Relationship between ore deposits in river catchments and geochemistry of suspended particulate matter from six rivers in southwest France

Here we present original data on the geochemical composition of fluvial particulate matter transported by the rivers of the Adour/Garonne basin, which drains one-fifth of the French land surface. Suspended particulate matter from the six main rivers in the basin, sampled at 'normal' flow and during a flood, is compared in terms of: grain size; particulate organic carbon; Fe; Mn; and trace element concentrations (e.g. Zn, Cd, Pb, Cu, Mo, Sn, Ni, Co, Cr, V, As, Hg, U, Th, W, Au, Ag, Ta). Three of the six studied rivers (Garonne, Dordogne and Isle Rivers) are the main tributaries of the Gironde estuary (southwest France), known for Cd pollution. The Adour and Gaves Rivers enter the Adour Estuary and the Charente River reaches the ocean by the Charente Estuary. Our data show, that Cd (and Zn) are not the only trace elements of eco-toxicological relevance transported into the Gulf of Biscay by these six rivers. Potentially toxic elements (e.g. As, Sn, U, Cu, Ag) show elevated concentrations in river particulates entering the estuaries, compared to world average concentrations [Martin and Whitfield, 1983, The significance of the river input of chemical elements to the oceans. In: C.S. Wong, E. Boyle, K.W. Bruland, J.D. Burton, E.D. Goldberg (editors), Trace Metals in Sea Water, Plenum, New York: pp. 265-296]. Comparing SPM sampled during 'normal' discharge and flood, the basin shows a distinct trace element composition of SPM mostly related to ore deposits in the upper basins (Massif Central and Pyreneans). This geochemical signal is partly masked during floods due to changes in grain size, but also due to increased erosion of the lower parts of the basins. This study proves pumping/centrifugation to be the most appropriate sampling/separation technique (recovery, representativity, contamination) by comparing different methods of SPM recovery.     

Survey of total and respirable suspended particulate matter in an iron foundry. Comparison of stationary sampling and personal monitoring

In the workshop of an iron foundry total and respirable suspended particulate matter was collected. The performances of (1) filtration systems with 47 mm membrane filters, (2) Andersen cascade impactors, and (3) personal total or respirable monitoring, were compared at a position away from intense sources of particulate debris.Using 15 stationary samplers a survey was made of the particulate levels in the workshop, over a period of 2 weeks. Very large concentration gradients and concentration variations as a function of time were measured for total suspended particulate matter.In the three major source areas, i.e. the pouring department, the core-making department and the shake-out department, special studies were performed to compare stationary and personal monitoring.In the immediate vicinity of intense point sources of coarse particles, such as core-making or shake-out, stationary sampling cannot be used to estimate the personal exposure to total suspended particulates. For respirable particles, however, one or two well-situated stationary size-selective samplers can provide a good estimate of the personal exposure as measured with a personal respirable monitor. The differences found are in the order of 10–20%.     

Acid extraction of lead and cadmium from newly-purchased ceramic and melamine dinnerware.

Imported dishes can present human health hazards in two ways: (1) dinnerware that contains toxic metals in excessive amounts may gain entry to the US; and (2) imported decorative ceramic plates may be improperly labeled regarding permissible use with food. In the present study, non-random samples of dishes were purchased in new condition in US retail outlets and subjected to 24-h acid leaching tests. Two of 28 patterns of imported ceramic dinnerware were found to release lead in levels that exceed US Food and Drug Administration (FDA) limits, and 10 other patterns released lead in concentrations exceeding California Proposition 65 (CA 65) limits. One imported ceramic dish released cadmium in excess of FDA limits. Samples of new foreign-made melamine (plastic) dinnerware in four patterns released neither lead nor cadmium in detectable concentrations. One of three patterns of imported decorative ceramic plates released lead in concentrations exceeding 2000 micrograms/ml. These plates are not permanently labeled as hazardous and are in noncompliance with FDA regulations.     

Characterisation of urban catchment suspended particulate matter (Auckland region, New Zealand); a comparison with non-urban SPM

Suspended particulate matter (SPM) is an important transport agent for metal contaminants in streams, particularly during high flow periods such as storm events. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal partitioning between the dissolved phase and SPM was determined, and SPM characterised in terms of its Si, Al, Fe, Mn, Zn, Cu, Pb, TOC, TON and PO(4) concentrations, as well as particle size, abundance, type and surface area. This data was compared to similar data from representative non-urban catchments in the Auckland region, the Kaipara River and Waikato River catchments, to identify any significant differences in the SPM and its potential trace metal adsorption capacity. Trace metal partitioning was assessed by way of a distribution coefficient: K(D)=[Me(SPM)]/[Me(DISS)]. Auckland urban SPM comprises quartz, feldspars and clay minerals, with Fe-oxides and minor Mn-oxides. No particles of anthropogenic origin, other than glass shards, were observed. No change in urban SPM particle size or SSA was observed with seasonal change in temperature, but the nature of the SPM was observed to change with flow regime. The abundance of finer particles, SSA and Al content of the SPM increased under moderate flow conditions; however, Si/Al ratios remained constant, confirming the importance of aluminosilicate detrital minerals in surface run-off. The SPM Fe content was observed to decrease with increased flow and was attributed to dilution of SPM Fe-oxide of groundwater origin. The Kaipara River SPM was found to be mineralogically, chemically and biologically similar to the urban SPM. However, major differences between urban catchment SPM and SPM from the much larger (non-urban) Waikato River were observed, and attributed to a higher abundance of diatoms. The Fe content of the Waikato River SPM was consistently lower (<5%), and the Si/Al ratio and Mn content was higher. Such differences observed between urban and non-urban SPM did not appear to affect the partitioning of Zn and Cu; however, Pb in the Kaipara and Waikato Rivers was found to be more associated with the dissolved phase. This is likely to reflect higher particulate Pb inputs to urban systems.     

Sources and properties of non-exhaust particulate matter from road traffic: a review

While emissions control regulation has led to a substantial reduction in exhaust emissions from road traffic, currently non-exhaust emissions from road vehicles are unabated. These include particles from brake wear, tyre wear, road surface abrasion and resuspension in the wake of passing traffic. Quantification of the magnitude of such emissions is problematic both in the laboratory and the field and the latter depends heavily upon a knowledge of the physical and chemical properties of non-exhaust particles. This review looks at each source in turn, reviewing the available information on the source materials and particles derived from them in laboratory studies. In a final section, some of the key publications dealing with measurements in road tunnels and the roadside environment are reviewed. It is concluded that with the exception of brake dust particles which may be identified from their copper (Cu) and antimony (Sb) content, unequivocal identification of particles from other sources is likely to prove extremely difficult, either because of the lack of suitable tracer elements or compounds, or because of the interactions between sources prior to the emission process. Even in the case of brake dust, problems will arise in distinguishing directly emitted particles from those arising from resuspension of deposited brake dust from the road surface, or that derived from entrainment of polluted roadside soils, either directly or as a component of road surface dust.     

Metal content of dandelion (Taraxacum officinale) leaves in relation to soil contamination and airborne particulate matter.

The global distribution of the common dandelion (Taraxacum officinale Weber, sensu lato; Asteraceae), along with its ability to tolerate a wide range of environmental conditions, make this 'species' a particularly attractive candidate to evaluate for its value as a biological monitor of environmental metal contamination. To examine the metal content of dandelion leaves in relation to environmental metal levels, the concentrations of eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were analyzed in leaf and soil samples collected at 29 sites in the mid-western United States differentially impacted by pollution. Sites were chosen primarily to cover a range of annual mean 24-h airborne particulate matter < or = 10 microm (hereafter, PM10) exposure, with PM10 levels varying from those found in isolated rural areas to levels typical of the most industrialized urban locations in the mid-western United States. A positive. significant correlation was detected between soil concentrations of each metal and measures of PM10 at a site, signifying that airborne particulate matter is a good indicator of soil metal contamination. Leaf concentrations of four of the eight metals (Cr, Mn, Pb and Zn) examined were found to increase significantly as the soil levels of these metals increased, but the percentage of the total variation explained by the relationship in these cases was generally low. This latter finding, along with the lack of a significant relationship between leaf and soil concentrations for the four other metals, indicate that the factors affecting metal absorption from the soil by dandelions are complex and that, aside from soil metal concentrations, other soil, plant and/or other environmental factors affect metal uptake. There was also no evidence that leaf metal concentrations were positively correlated with PM10. In addition, the concentrations of some metals (Cu, Fe, Mn, Pb and Zn) were significantly higher in leaves collected in the fall compared to those collected at the same sites in the spring. These findings suggest that dandelions may not be a particularly effective tool for quantifying levels of environmental metal contamination, at least on the scale of pollution typifying industrialized urban areas of the mid-western United States.     

室内颗粒物的来源和特点研究

分析了国内外在室内颗粒物的来源和室内外颗粒源对室内颗粒物浓度的影响方面的研究进展。指出了目前研究中存在的问题,并对未来的研究方向进行了展望。     

The significance of cadmium in hair. The influence of a recommended washing procedure on the cadmium content of hair of rats experimentally exposed to cadmium

The impact of a "mild" preanalytical washing procedure on an elevated Cd-content in hair was studied in newly grown hair of rats exposed to a large amount of Cd in their drinking water. A large part of the Cd in hair was removed by this procedure. Agitation by way of ultrasound seems to be no more effective than agitation by mechanical shaking. The effectiveness of washing varied in accordance with the type and duration of exposure.