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.     

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.     

Use of biomass sorbents for oil removal from gas station runoff

The use of biomass sorbents, which are less expensive and more biodegradable than synthetic sorbents, for oil removal from gas station runoff was investigated. A bench-scale flume experiment was conducted to evaluate the oil removal and retention capabilities of the biomass sorbents which included kapok fiber, cattail fiber, Salvinia sp., wood chip, rice husk, coconut husk, and bagasse. Polyester fiber, a commercial synthetic sorbent, was also experimented for comparison purpose. Oil sorption and desorption tests were performed at a water flow rate of 20 lmin-1. In the oil sorption tests, a 50 mgl(-1) of used engine oil-water mixture was synthesized to simulate the gas station runoff. The mass of oil sorbed for all sorbents, except coconut husk and bagasse, was greater than 70%. Cattail fiber and polyester fiber were the sorbents that provided the least average effluent oil concentrations. Oil selectivity (hydrophobic properties) and physical characteristics of the sorbents are the two main factors that influence the oil sorption capability. The used sorbents from the sorption tests were employed in the desorption tests. Results indicated that oil leached out of all the sorbents tested. Polyester fiber released the highest amount of oil, approximately 4% (mass basis) of the oil sorbed.     

Effects of spent lubricating oil on the growth of Capsicum annum L. and Lycopersicon esculentum Miller

Susceptibility of the hot pepper (Capsicum annum L.) and the tomato (Lycopersicon esculentum Miller) to spent lubricating oil was investigated in soils supplemented with concentrations of oil ranging from 1-5% w/w. Treatment of soil with 4 and 5% spent oil consistently inhibited germination of both crops. Eighty-four days after sowing, the mean height and leaf area of C. annum in soil treated with 3% spent oil gave the lowest values. These were 3.14 +/- 0.6 cm and 0.24 +/- 0.01 cm(2) compared with respective values of 19.2 +/- 0.2 cm and 2.9 +/- 0.3 cm(2) for control plants. Premature death was observed in the case of L. esculentum plants treated with all tested strengths of spent lubricating oil.     

An evaluation of olive-tree bark for the biological monitoring of airborne trace-elements at ground level

There is a need to start looking into the possibility of tree bark for biomonitoring. Bark from olive trees (Olea europaea Linn.) has been collected over an area in northwestern Portugal, featuring a blend of rural lands, industrial towns and coastal environments. Samples were analysed through INAA and PIXE for their elemental contents. Results from both techniques were reconciled and then compared with an extensive database on 46 trace elements in Parmelia spp. thalli from the same sites and mostly from the very bark substrates. Distribution-free, nonparametric statistics show that, despite signal magnitude, variation patterns of bark and lichen concentrations follow one another in a most significant way. Selected elements in bark also correlate to a superior extent. As far as this investigation goes, there is no reason whatsoever for discarding bark as an alternative to lower epiphytes.     

The removal of heavy metals in urban runoff by sorption on mulch

A series of adsorption experiments was conducted in order to assess the ability of three mulches to remove several of the heavy metal ions typically encountered in urban runoff. Three types of mulch, cypress bark (C), hardwood bark (H), and pine bark nugget (P), were selected as potential sorbents to capture heavy metals in urban runoff. The hardwood bark (H) mulch had the best physicochemical properties for adsorption of heavy metal ions. In addition, because of its fast removal rate and acceptably high capacity for all the heavy metal ions, it was concluded that the H mulch is the best of the three adsorbents for treatment of urban runoff containing trace amounts of heavy metals. In order to investigate the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The sorption of these metals on H mulch conformed to the linear form of the Langmuir adsorption equation. At pH 5 and 6, the Langmuir constants (S(m)) for each metal were found to be 0.324 and 0.359 mmol/g (Cu); 0.306 and 0.350 mmol/g (Pb); and 0.185 and 0.187 mmol/g (Zn) at 25 degrees C.     

内电解法处理含N,N-二甲基乙酰胺工业废水

用内电解法处理含N,N-二甲基乙酰胺(DMAC)工业废水,研究pH、Fe∶C(体积比)、活性炭粒径和水力停留时间(HRT)等对该废水处理效果的影响,并确定最佳工艺条件。实验结果表明:在进水浓度维持在50 mg/L左右,最佳的工艺参数pH、Fe∶C和HRT分别为3.0、1∶1和60 min时,DMAC去除率高达到95%,处理水DMAC浓度小于5 mg/L。处理后废水的可生化性有明显的改善,BOD5/COD由0.21提高至0.66;而DMAC的去除基本符合二级动力学规律。     

包埋水华鱼腥藻和活性炭对污水中氮磷的净化

采用聚乙烯醇-海藻酸钠（PVA—SA）凝胶包埋水华鱼腥藻与活性炭混合物,对比水华鱼腥藻在包埋、吸附以及悬浮状态下对高浓度模拟废水中氨氮的去除效果,实验结果表明,水华鱼腥藻在包埋状态下对氨氮有更好的去除效果。通过正交实验研究SA、粉末活性炭（PAC）、水华鱼腥藻之间不同质量比的包埋混合物对去除污水中NH4＋-N、TP以及处理后废水中微囊藻毒素（MC）残留量的影响,结果表明,当PVA量为8％时,SA、PAC和藻含量分别在0．5％、0．5％和0．2％为NH4＋-N、TP的最佳去除组合,同时处理后污水中MC的含量也低于联合国标准1Iμg／L,避免了二次污染的同时为产毒素藻类的利用创造了条件。     

Chemical composition and ecophysiological responses of Empetrum nigrum to aboveground element application

Empetrum nigrum L. (crowberry) is one of the plants surviving near the Cu-Ni smelters in Finland and Russia. According to field observations, the fine roots of E. nigrum are situated below 40 cm depth and the root biomass is reduced in the polluted sites. This could cause a reduced root uptake of macronutrients and trace elements in the field and, therefore, the possible element uptake by aboveground parts of E. nigrum was studied in a greenhouse. Six different treatment solutions containing various heavy metal and macronutrient concentrations were applied to the stems and leaves of E. nigrum and the chemical composition and ecophysiological parameters were measured. Heavy metal concentrations in the leaves and stem bark, and Cu concentrations in the stems, increased with increasing metal concentrations in the spraying solutions. The bark and leaves had higher heavy metal concentrations than the stems of comparable age classes. The macronutrient and Mn concentrations in E. nigrum did not change significantly with increasing element concentrations in the spraying solution. Neither the stem water potential nor the leaf chlorophyll concentrations showed any clear response to element applications. Therefore, the element uptake by aboveground parts of E. nigrum was not confirmed by this study. However, there was a tendency to a decrease in CO2 exchange rate and increase in foliar abscisic acid content in plants treated with the highest element concentrations.     

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.     

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.     

Enhanced reductive dechlorination in columns treated with edible oil emulsion

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.     

TiO2光催化-微滤膜分离深度净化亚甲基蓝印染废水

采用悬浮式TiO2光催化膜反应器深度净化纺织工业园区含亚甲基蓝印染废水经生物处理二级出水,利用中空纤维微滤膜进行催化剂截留分离,研究催化剂投加量、运行时间、溶解氧、搅拌方式对出水水质及膜通量的影响。结果表明:光催化会消耗体系溶解氧,鼓风曝气搅拌可同时为系统供氧,优于机械搅拌;该耦合体系的催化剂最佳投加量为1 g/L,经光催化氧化-膜组合工艺处理后水质优于GB 4287-1992《纺织染整工业污染物排放标准》的I级标准,符合建设部颁布的《生活杂用水水质标准》(CJ/T 48-1999)。     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

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.     

Baseline concentrations of elements in the Antarctic macrolichen Umbilicaria decussata

Total concentrations of major and trace elements were determined in samples of the epilithic lichen Umbilicaria decussata from 24 ice-free areas in coastal Victoria Land (Antarctica). Overall average concentrations of trace elements except Cd were the lowest ever reported for lichens of the genus Umbilicaria. Specifically, the mean level of Pb in lichens from granitic rocks (0.46 +/- 0.18 microg g(-1) dry wt) was more than four times lower than the lowest record in Arctic lichens. No impact of local human activities was detected, but the elemental composition of U. decussata was affected by entrapment of soil or rock dust particles and probably by uptake of soluble elements from substrate. Relationships between elements and their distribution patterns in the study area indicated that the marine environment is the main source of major ions and perhaps of Cd in lichens. Accumulation of P was detected in samples from coastal sites frequented by seabirds. Although the present results can be taken as baseline levels of major and trace elements in Antarctic U. decussata from substrates with very different geochemical features, further research is necessary to evaluate the relative element contribution from each substrate with respect to those from snow, marine aerosol, salt encrustations and guano.     

Metal biomonitoring with mosses in the surroundings of an oil-fired power plant in Italy

Levels of 12 trace elements were measured in samples of the bryophyte Hypnum cupressiforme Hedw. and in soil collected in the surroundings of an oil-fired power plant in Northern Italy. Metal bioaccumulation in moss was estimated after soil correction in order to obtain deposition patterns and individuate potentially toxic metals emitted from the plant. V and Ni, occurring together in fuel oil, showed highest bioaccumulation values near the stacks. Mean contamination of the study area for these elements is 5.5 (V) and 3.3 (Ni) times the background levels of the reference site. Other elements showed only limited alterations of bioaccumulation values, in relation to agricultural and industrial activity in the study area.     

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.     

预涂动态膜强化渗透与截留性能研究

以二氧化钛粉体材料为涂膜剂,陶瓷管为基膜制备预涂动态膜,引入通量增强系数Zi和截留增强系数Fi研究了预涂动态膜制备条件对其强化渗透与截留性能的影响,并用SEM电镜对预涂动态膜和基膜表面形貌进行表征。结果表明:制备的预涂动态膜表面均匀密实,其孔径低于基膜平均孔径。预涂动态膜的渗透与截留性能随涂膜液pH值的增加而增加,在跨膜压差低于0.2 MPa、错流速度低于1.5 m/s,涂膜时间少于30 m in和涂膜液浓度低于0.4 g/L范围内,提高这些参数值有利于提高预涂动态膜的渗透与截留性能,超出此范围时,提高这些参数值对增强其渗透与截留性能的效果已不明显,其中错流速度的影响相对小些。跨膜压差为0.2 MPa,错流速度为1.5 m/s,涂膜时间30 m in,涂膜液浓度和pH值分别为0.4 g/L和10.2时为最佳制备条件。