Removal of hydrocarbons from wastewater using treated bark

This paper explores the possibility of removing hydrocarbons (HCs) and trace elements from synthetic and industrial effluents using treated bark as biosorbent. Coniferous bark was treated either chemically (Tc) or biologically (Tb) to eliminate soluble organic compounds of bark. The removal efficiency (RE) of the HCs from a synthetic oil-water mixture containing spent diesel motor oil exceeds 95% using 2 g/L of treated bark mixed with a synthetic oil-water mixture containing 2 g/L of spent oil. Under these conditions, the retention capacity (RC) was approximately 1 g HC/g dry substrate. The sorption reaction seems to be quasi-instantaneous, and the retention capacity of spent oil on treated bark increases as the temperature augments. This implies that the retention mechanism is related to the capillary action. Results of Fourier transform infrared (FTIR) spectroscopy indicate that spent oil is mainly composed of alkanes. They also suggest that no chemical bonds between Tc and spent oil were established. Measurement of the surface tension of spent oil and the wetting index of the bark suggests that only spent oil will be retained by the substrate. Treatment of an industrial effluent containing 14.4 g/L of total HCs was performed using Tc. It was possible to remove 97% of HCs and retain some trace elements such as Al, Ca, Fe, Mg, S, and so on.     

Removal of Hydrocarbons from Wastewater Using Treated Bark

ABSTRACT

This paper explores the possibility of removing hydrocarbons (HCs) and trace elements from synthetic and industrial effluents using treated bark as biosorbent. Coniferous bark was treated either chemically (Tc) or biologically (Tb) to eliminate soluble organic compounds of bark. The removal efficiency (RE) of the HCs from a synthetic oil-water mixture containing spent diesel motor oil exceeds 95% using 2 g/L of treated bark mixed with a synthetic oil-water mixture containing 2 g/L of spent oil. Under these conditions, the retention capacity (RC) was ~1 g HC/g dry substrate. The sorption reaction seems to be quasi-instantaneous, and the retention capacity of spent oil on treated bark increases as the temperature augments. This implies that the retention mechanism is related to the capillary action.

Results of Fourier transform infrared (FTIR) spectros-copy indicate that spent oil is mainly composed of al-kanes. They also suggest that no chemical bonds between

Tc and spent oil were established. Measurement of the surface tension of spent oil and the wetting index of the bark suggests that only spent oil will be retained by the substrate. Treatment of an industrial effluent containing 14.4 g/L of total HCs was performed using Tc. It was possible to remove 97% of HCs and retain some trace elements such as Al, Ca, Fe, Mg, S, and so on.     

Accumulation of Mn and Pb in linden (Tilia platyphyllos Scop.) bark and wood

As an indicator of environmental pollution, we collected tree rings and bark of linden (Tilia platyphyllos Scop.) from four sampling locations in Serbia. Mn and Pb were determined with a spectrochemical method that has an argon-stabilized U-shaped DC arc with aerosol supply as excitation source. Increased concentrations of Mn in linden tree rings and bark were found at the Debeli Lug location, where the Mn transfer factors were largest. The availability of Mn in soil and tree rings was greatly influenced by pH. Since 1950, Mn level decreased more noticeably on acidic soils. Higher concentrations of Pb were found in linden tree rings and bark at the locations Fru?ka Gora and Zemun. Proximity of the road to Novi Sad at both sites may be a possible reason for this. The Pb transfer factor was highest at Fru?ka Gora. The ratio of bioavailable elements in soil for Mn and Pb were also calculated. Close correlations between Mn and Pb concentrations in linden tree rings and the ratio of bioavailable elements in soil were seen at all four locations.     

The use of SEM/EDX for studying the distribution of air pollutants in the surroundings of the emission source

A new application of SEM/EDX-methods to study the distribution of air pollutants in the surroundings of an emission source is described. An energy dispersive X-ray microanalyzer (EDX) connected to a scanning electron microscope (SEM) was used to measure the amount of several elements on the surface of Scots pine bark. To test this method, bark samples were collected near a limestone quarry and plant. The results indicated that the pollutant gradient in the surroundings of the emission source was clearest, when this new method was used. The coefficient of determination (R2) for calcium on pine bark was as high as 0.99, whereas in the same study line, measurements of total Ca content of pine needles and soil humus yielded R2 values of 0.46 and 0.74, respectively.     

Elemental levels in tree-bark and epiphytic-lichen transplants at a mixed environment in mainland Portugal, and comparisons with an in situ lichen

Samples of Platanus hybrida Brot. bark and Flavoparmelia caperata (L.) Hale thalli, from a clean area in northern Portugal (Bai?o), were transplanted into an exposure location at the south-western Atlantic coast, impacted by urban-industrial emissions (Sines), for a 10-month long experiment. Bark pieces were confined into nylon bags (2-mm mesh), and lichen thalli kept with their bark substrate (Pinus pinaster (Ait.) Sol.). Every two months, a double set of transplants (one for bark, one for lichens) was brought back into the laboratory, together with native samples of Evernia prunastri (L.) Ach. Following suitable cleansing and preparation procedures, field samples were put through INAA for elemental assessment. The results indicate that, regardless of signal magnitude, (1) concentrations in bark and lichen transplants are significantly correlated with atmospheric deposition for an appreciable number of elements; (2) there are a number of significant correlations between transplanted and native samples, and again between the latter and the deposition; and (3) the elements with biological patterns that follow the deposition in either transplanted or native samples (Co, V) are the very ones whose bioaccumulation seems to benefit from an alternation of wet-dry periods, which fits the precipitation record of the test site during the exposure term.     

Self-organizing feature map (neural networks) as a tool to select the best indicator of road traffic pollution (soil, leaves or bark of Robinia pseudoacacia L.)

Concentrations of the elements Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in the leaves and bark of Robinia pseudoacacia and the soil in which it grew, in the town of Ole?nica (SW Poland) and at a control site. We selected this town because emission from motor vehicles is practically the only source of air pollution, and it seemed interesting to evaluate its influence on soil and plants. The self-organizing feature map (SOFM) yielded distinct groups of soils and R. pseudoacacia leaves and bark, depending on traffic intensity. Only the map classifying bark samples identified an additional group of highly polluted sites along the main highway from Wroc?aw to Warszawa. The bark of R. pseudoacacia seems to be a better bioindicator of long-term cumulative traffic pollution in the investigated area, while leaves are good indicators of short-term seasonal accumulation trends.     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.     

Biomonitoring using the lichen Hypogymnia physodes and bark samples near Zlatna, Romania immediately following closure of a copper ore-processing plant

Lichen transplants were established along a 40km transect centred on a large mine waste dump close to Zlatna town centre, two weeks after closure of a major industrial source, to compare spatial patterns of element concentrations in lichen and bark samples. After 3 months of exposure, spatial patterns of 4 element concentrations (Pb, Cu, Zn and Fe) in transplants confirmed deposition due to a point source 'Zlatna influence'. Cu and Pb reached concentrations 8 and 4 times, respectively, higher than samples transplanted in the 'background' site, and over 200 (Cu) and 2000 (Pb) times higher relative to 'background' bark. Ten out of 15 elements analysed reached highest concentrations in bark. Spatial patterns confirmed long-term pollution for 6 elements (Pb, S, Fe, Cu, Zn and Ba). The study provides a model baseline to monitor recovery following closure of major industrial sources and highlights the importance of considering biogeochemical processes when interpreting metal concentrations.     

Use of treated bark for the removal of lipids from water

Raw, biologically treated bark and bark impregnated with transition metal ions were used to retain the lipids from synthetic emulsions. Several experimental parameters affecting the lipid removal efficiency (RE) were studied (initial concentration of lipids, temperature, time, pH, carboxylic acid chain length, etc.). Saturated bark was characterized using Fourier transform infrared (FTIR) spectroscopy and light microscopy, and the treated bark wetting index was determined. Results show that lipid removal can exceed 95% of the initial concentration at a pH lower than 7. The uptake of lipids by these sorbents varied from 0.2 to 2.5 g/g of dry bark. Trials for regenerating the sorbent saturated by lipids allowed the recovery of approximately 95% of lipids. The calorific value of the saturated bark was approximately 79% that of domestic fuel and can be considered as an energy source, thus avoiding its waste disposal. These results may upgrade the treatment of wastewater generated by several industrial sectors, such as the food industry, surface treatment, and so on.     

Trees as bioindicator of heavy metal pollution in three European cities

Concentrations of four heavy metals were determined in tree leaves and bark collected from polluted and non-polluted areas of three European cities (Salzburg, Belgrade and Thessaloniki) for a comparative study. Platanus orientalis L. and Pinus nigra Arn., widespread in urban northern and southern Europe, were tested for their suitability for air quality biomonitoring. Leaves and barks were collected uniformly of an initial quantity of about 30 g of each sample. Analysis was accomplished by electrothermal atomic absorption spectrometry after total digestion. Site-dependent variations were found with the highest concentration level measured in Belgrade, followed by Thessaloniki and Salzburg. A higher accumulation of heavy metals was found in bark compared to leaves. Pine tree bark, accumulating higher concentrations of trace metals compared to plane tree bark, shows a higher efficiency as bioindicator for urban pollution. Both indicator species are suitable for comparative studies on bioindication of urban air pollution.     

Heavy metals in bark of <Emphasis Type="Italic">Pinus massoniana</Emphasis> (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang,China

Goal, Scope and Background Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Methods Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO₃. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0–10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Results and Discussion Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Conclusions Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. Recommendations and Perspectives The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.     

Assessment of airborne heavy metal pollution by aboveground plant parts

Italian stone pine (Pinus pinea L.) and oleander (Nerium oleander L.) leaves, bark and wood samples were collected at different sites around an industrial area (Huelva, SW Spain) and compared with samples of the same species from a background site. Samples were analysed with respect to the following pollutants: Al, Ba, Cr, Cu, Fe and Pb by ICP-AES. The suitability of different plant parts as biomonitors of pollution was investigated. In pine samples from the polluted sites the ratio of concentrations between bark and wood was high for Al, Ba, Cu and Fe, whereas no differences were found in samples from the unpolluted area. No differences were detected in oleander for the same ratio. In the oleander species, the ratio between leaves and wood concentration allowed to distinguish between control and polluted sites. The ratio of the concentration between leaves and wood was elevated for Al, Ba and Fe in pine samples from the polluted sites. The ratio of the concentration in bark or leaves to their concentration in wood might be useful to detect inorganic atmospheric pollutants.     

Iron content and its relations to the sulphur and titanium contents of epiphytic and terricolous lichens and pine bark in Finland

The iron content was studied in the epiphytic lichens Hypogymnia physodes (L.) Nyl. and Pseudevernia furfuracea (L.) Zopf, in the terricolous lichens Cladina sp. and Peltigera aphthosa (L.) Willd., and in pine bark collected from 31 sites in Finland. There appeared to be differences between lichen species, epiphytes having generally higher concentrations. The iron content of H. physodes was highly significantly correlated (p<0.001) with its sulphur content, reflecting the relations of these elements in precipitation. The highly significant correlations between the iron and titanium contents indicated differences of the phorophytes. The iron/sulphur ratio of H. physodes on pine was 1.3 and on birch 1.4 and iron/titanium ratios were 10.4 and 11.3 respectively. The iron content of Cladina sp. showed highly significant parallel correlations (p<0.001) with its sulphur and titanium contents. The iron/titanium ratio decreased from 9.6 to 8.2 when the iron content increased by 95%, the sulphur content being equal. The iron/titanium ratio of Cladina sp. was nearly identical to that of P. furfuracea. The relation between iron and sulphur, and the fraction of soluble and insoluble iron in precipitation versus lichens and pine bark were considered. Special attention was paid in the discussion to differences in substrate: pine and birch bark for H. physodes, and soil for Cladina sp.     

Mapping aerial metal deposition in metropolitan areas from tree bark: a case study in Sheffield, England

We investigated the use of metals accumulated on tree bark for mapping their deposition across metropolitan Sheffield by sampling 642 trees of three common species. Mean concentrations of metals were generally an order of magnitude greater than in samples from a remote uncontaminated site. We found trivially small differences among tree species with respect to metal concentrations on bark, and in subsequent statistical analyses did not discriminate between them. We mapped the concentrations of As, Cd and Ni by lognormal universal kriging using parameters estimated by residual maximum likelihood (REML). The concentrations of Ni and Cd were greatest close to a large steel works, their probable source, and declined markedly within 500 m of it and from there more gradually over several kilometres. Arsenic was much more evenly distributed, probably as a result of locally mined coal burned in domestic fires for many years. Tree bark seems to integrate airborne pollution over time, and our findings show that sampling and analysing it are cost-effective means of mapping and identifying sources.     

The anthropogenic atmospheric elements fraction: A new interpretation of elemental deposits on tree barks

The superficial deposit on the bark surface of several trees (mainly Fraxinus excelsior L.) was sampled in the experimental station of the university campus in Grenoble (France). Its composition was studied by scanning electron microscopy–energy dispersive X-ray emission (SEM–EDX) and, after digestion, by inductively coupled plasma-mass spectrometry (ICP-MS). The deposit was composed of 81.3% ± 7.4 organic matter, 9.4% ± 4.9 of geogenic minerals issued from the atmosphere (atmospheric geogenic fraction: AGF) and 9.3% ± 2.7 of a mixture of elements which was called anthropogenic atmospheric elements fraction (AAEF). The SEM–EDX analysis showed the presence of particles of geogenic compounds such as different types of silicates, phosphates, carbonates, sulphates, oxides and also particles of metals such as iron or of alloys of Fe–Zn, Fe–Ni, Ni–Cr and Ca sulphates or phosphates. Typical spheres of “fly ashes” composed of pure iron or Al-silicates were detected. Using the SEM–EDX analysis of the deposit and the average local soil composition, an empiric formula for the AGF (without polluting elements) was chosen, which presented a clear analogy with the global formula of the upper continental crust. In the same way, a formula for the pure organic matter fraction was chosen. Withdrawing the elements corresponding to these two fractions allows a tentative estimation of the content of the AAEF which was supposed to better represent the elemental anthropogenic contamination issued from the atmosphere. In the station, most of Sb, Cd, Sn, Pb, Cu, V and Zn were found in the AAEF. This AAEF composition was compared to that of the deposit in a highway tunnel where Pb and Cu were at a very high level. The meaning and the limits of the AAEF concept were critically discussed.     

Airborne uranium contamination--as revealed through elemental and isotopic analysis of tree bark

A new strategy for characterisation of airborne uranium contamination based on ICP mass spectrometric analysis of tree bark is described. The uranium content of tree barks (50 samples) obtained from diverse locations (remote, rural, industrial) varied over almost four orders of magnitude (0.001-8.3 micrograms/g U) with maximum concentrations recorded in the vicinity of a nuclear fuel fabrication plant (0.70-8.3 micrograms/g U). Elevated concentrations were also observed near a coal-fired power station (0.25-0.38 microgram/g U). Isotopic analysis revealed significant deviation from the natural uranium isotope ratio (235U/238U, 0.00725) at four nuclear installations (235U/238U, 0.0055-0.0097). These findings indicate that tree bark serves as an effective biomonitor for uranium and, with isotopic analysis, discrimination between nuclear and non-nuclear emissions is realised.     

Sorption of pentachlorophenol on pine bark

The minimization of pentachlorophenol (PCP) transport in the environment driven by industrial wastewater discharges can be accomplished by sorption in natural, available and low cost by-products like pine bark. Taking into account that PCP is a chemical which behaviour is highly dominated by the surrounding features, this work intended to evaluate the sorption kinetics and equilibrium parameters according to the pH and temperature as well as the pine bark particle size. The PCP uptake by pine bark showed to be faster in the initial phase followed by a slower process, being 24 h the suitably time to reach the sorption equilibrium in the range of pH studied. The neutral PCP species showed to have higher binding capacity to pine bark than the anionic PCP, which was reflected in a decrease in the distribution coefficient (Kd) of the linear sorption isotherm with the increase of solution pH from 2 to 7. On the other hand, between 10 degrees C and 35 degrees C, the temperature does not seem to play a significant role in the PCP sorption by pine bark, while the sorbent size is a key parameter to enhance the overall process.     

Levels of polybrominated diphenyl ethers and hexabromocyclododecane in the atmosphere and tree bark from Beijing, China

Air samples in four seasons at one site and tree bark samples from four districts were determined to investigate seasonal variation and regional distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in Beijing, China. The total concentrations of PBDEs (∑PBDE) and HBCD (∑HBCD) were in the range of 57-470 and 20-1800 pg m⁻³ in the atmosphere, respectively. The ∑PBDE and ∑HBCD concentrations were significantly influenced by the total suspended particulate matter in atmosphere. The total concentrations of PBDEs and HBCD in tree bark samples were in the range of 99-3700 and 26-3400 ng g⁻¹ lipid weight. It was found that regional distribution of PBDEs and HBCD was related to the function of each district. In addition, the study found that weeping willow bark was an ideal atmospheric PBDEs and HBCD passive sampler. Finally, atmospheric levels of BDE-209 and HBCD at tree bark sampling districts were estimated via applying an established bark/air partitioning model, which had been verified by the measured concentrations in tree bark and atmosphere in Beijing.     

Tree bark as a passive air sampler to indicate atmospheric polybrominated diphenyl ethers (PBDEs) in southeastern China

The different barks were sampled to discuss the influence of the tree species, trunk circumference, and bark thickness on the accumulation processes of polybrominated diphenyl ethers (PBDEs) from air into the bark. The results of different PBDE concentrations indicated that barks with a thickness of 0–3 mm collected from weeping willow, Camphor tree, and Masson pine, the trunk circumferences of which were 100 to 150 cm, were better PBDEs passive samplers. Furthermore, tree bark and the corresponding air samples were collected at Anji (AJ), Hangzhou (HZ), Shanghai (SH), and Wenling (WL) to investigate the relationship between the PBDE concentrations in bark and those in air. In addition, the significant correlation (r ²?=?0.906; P?<?0.05) indicated that atmospheric PBDEs were the principle source for the accumulation of PBDEs in the barks. In this study, the log K _BA (bark–air partition coefficient) of individual PBDE congeners at the four sites were in the range from 5.69 to 6.79. Finally, the total PBDE concentration in WL was 5 to 20 times higher than in the other three cities. The result indicated that crude household workshops contributed a heavy amount of PBDEs pollution to the environment, which had been verified by the spatial distribution of PBDEs levels in barks collected at Wenling (range, 26.53–1317.68 ng/g dw). The good correlation between the PBDE concentrations in the barks and the air samples and the variations of the PBDE concentrations in tree barks collected from different sites reflected that the bark could be used as a passive sampler to indicate the atmospheric PBDEs.     

Uptake of 207Pb and 111Cd through bark of mature sugar maple,white ash and white pine: a field experiment

A field study was undertaken to determine whether 207Pb and 111Cd, applied to the exterior bark of sugar maple (Acer saccharum Marsh.), white ash (Fraxinus americana L.) and white pine (Pinus strobus L.), could enter xylem tissue. Stable isotope tracers (3 microg Pb ml(-1); 2 microg Cd ml(-1)) were applied separately to bark in simulated rainfall, acidified to pH 4.5, in multiple doses over a 4 month (July-October) period. Tree cores were extracted from the region of application in the following March, and Pb and Cd isotopes were measured in bark and the outer tree rings using inductively coupled plasma mass spectrometry. The majority of the applied stable isotope tracer recovered (over 94%) was present in bark tissue, although a small amount of each metal tracer entered the outer (1-3) tree rings in all trees. Despite high concentrations of excess 207Pb in bark (up to 50 microg g(-1)), the maximum concentration of excess 207Pb measured in tree rings was only around 50 ng g(-1), which represents less than 30% of the background Pb concentration in wood at the study site. High excess 111Cd concentrations in bark (up to 35 microg g(-1)) also resulted in small increases in 111Cd in wood (up to 50 ng g(-1)), but due to lower background Cd concentrations in wood, such increases more than doubled the amount of Cd in wood compared with background levels. However, at sites where such high bark Cd concentrations are found, uptake from Cd-contaminated soil would probably be much greater than found at our study site. It appears that Cd and Pb applied to bark can enter woody tissue, but that this route of uptake is likely to be a minor contributor to the metal burden in wood.