Potential of biological materials for removing heavy metals from wastewater

Agricultural products/by-products are natural sorbent materials that possess capacity for removing contaminants including heavy metals from wastewaters and hence can be exploited as replacement of costly methods for wastewater treatment. The sorption of heavy metals onto these biomaterials is attributed to constituent's proteins, carbohydrates, and phenolic compounds that contain functional groups such as carboxylate, hydroxyl, and amine. Natural efficiency of these materials for removing heavy metals can be enhanced by treating them with chemicals. The present review emphasizes their use in developing eco-friendly technology for a large-scale treatment of wastewater.     

Removal of organic compounds during treating printing and dyeing wastewater of different process units

Wastewater in Shaoxing wastewater treatment plant (SWWTP) is composed of more than 90% dyeing and printing wastewater with high pH and sulfate. Through a combination process of anaerobic acidogenic [hydraulic retention time (HRT) of 15h], aerobic (HRT of 20h) and flocculation-precipitation, the total COD removal efficiency was up to 91%. But COD removal efficiency in anaerobic acidogenic unit was only 4%. As a comparison, the COD removal efficiency was up to 35% in the pilot-scale upflow anaerobic sludge bed (UASB) reactor (HRT of 15h). GC-MS analysis showed that the response abundance of these wastewater samples decreased with their removal of COD. A main component of the raw influent was long-chain n-alkanes. The final effluent of SWWTP had only four types of alkanes. After anaerobic unit at SWWTP, the mass percentage of total alkanes to total organic compounds was slightly decreased while its categories increased. But in the UASB, alkanes categories could be removed by 75%. Caffeine as a chemical marker could be detected only in the effluent of the aerobic process. Quantitative analysis was given. These results demonstrated that GC-MS analysis could provide an insight to the measurement of organic compounds removal.     

Contamination by butyltin compounds and organochlorine residues in green mussel (Perna viridis, L.) from Thailand coastal waters

In order to elucidate marine pollution by butyltins and organochlorine residues in coastal waters of Thailand, green mussels (Perna viridis) were collected in 1994 and 1995 and analyzed. Butyltin compounds, such as tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT), were detected in most mussel samples, ranging from 4 to 800 ng g(-1) wet wt (as total). The composition of butyltin derivatives in green mussel was in the order of TBT > DBT > MBT. The results indicated that butyltin contamination was widespread, particularly in high boating areas and in coastal aquaculture facilities. Concentrations of organochlorine residues were much lower than of butyltin compounds. Among organochlorine residues examined, dichlorodiphenyltrichloroethane compounds (DDTs) were found to be the highest, followed by polychlorinated biphenyls (PCBs) > chlordane compounds (CHLs) > hexachlorocyclohexanes (HCHs) > hexachlorobenzene (HCB). To our knowledge, this is a first report on the detection of butyltin residues in Thailand coastal waters.     

Decomposition of organochlorine compounds in flue gas from municipal solid waste incinerators using natural and activated acid clays

High-temperature particle control (HTPC) using a ceramic filter is a dust collection method without inefficient cooling and reheating of flue gas treatment; thus, its use is expected to improve the energy recovery efficiency of municipal solid waste incinerators (MSWIs). However, there are concerns regarding de novo synthesis and a decrease in the adsorptive removal efficiency of dioxins (DXNs) at approximately 300°C. In this study, the effect of natural and activated acid clays on the decomposition of monochlorobenzene (MCB), one of the organochlorine compounds in MSW flue gas, was investigated. From the results of MCB removal tests at 30–300°C, the clays were classified as adsorption, decomposition, and low removal types. More than half of the clays (four kinds of natural acid clays and two kinds of activated acid clays) were of the decomposition type. In addition, the presence of Cl atoms detached from MCB was confirmed by washing the clay used in the MCB removal test at 300°C. Activated acid clay was expected to have high dechlorination performance because of its proton-rich-composition, but only two clays were classed as decomposition type. Conversely, all the natural acid clays used in this work were of the decomposition type, which contained relatively higher di- and trivalent metal oxides such as Al₂O₃, Fe₂O₃, MgO, and CaO. These metal oxides might contribute to the catalytic dechlorination of MCB at 300°C. Therefore, natural and activated acid clays can be used as alternatives for activated carbon at 300°C to remove organochloride compounds such as DXNs. Their utilization is expected to mitigate the latent risks related to the adoption of HTPC, and also to contribute to the improvement of energy recovery efficiency of MSWI.

ImplicationsThe effect of natural and activated acid clays on MCB decomposition was investigated to evaluate their suitability as materials for the removal of organochlorine compounds, such as DXNs, from MSWI flue gas at approximately 300°C. More than half of the clays used in this study showed the decomposition characteristics of MCB. The presence of Cl atoms in the clay used in the MCB removal test at 300°C proved the occurrence of MCB decomposition. The results of this study suggest a novel flue gas treatment method to establish high-energy efficient MSWI systems.     

气相色谱/质谱测定苯酚丙酮生产废水中半挥发性有机物

建立了用二氯甲烷液液萃取对苯酚丙酮生产废水进行预处理,气相色谱/质谱法同时测定废水中半挥发性有毒有机物异丁酸、异丙苯、α-甲基苯乙烯、2-苯基丙醛、苯乙酮、2-苯基-2-丙醇、α-甲基苯甲醇、苯酚和苯甲酸等的定性定量分析方法。色谱条件为:DB-17MS型色谱柱,程序升温,进样量为1μL,质量选择检测器(MSD)。实验结果表明,该色谱条件对苯酚丙酮生产废水中各半挥发性组分具有较好的分离效果。而对9种组分的最低检出限均低于0.04mg/L,精密度实验相对标准偏差2.14%～5.15%,实际水样的加标回收率稳定。苯酚丙酮生产废水中的主要污染物为2-苯基-2-丙醇,其次为苯酚、异丁酸和异丙苯。     

生物膜反应器连续处理餐饮废水

用生物膜反应器连续处理餐水能有效降低废水中的ＢＯＤ及ＣＯＤ浓度。研究了水力停留时间对有机物去除率的影响,结果表明当水力停留时间大于７．８ｈ时,废水的ＣＯＤ,ＢＯＤ及ＴＳＳ的去除率均高于９０％。实验操作时,水力停留时间应略大于５．７ｈ。     

Incidence of chlorinated benzenes and chlorinated ethylenes in Lake Ontario Herring Gulls

Great Lakes Herring Gulls (Larus argentatus) and their eggs have proven to be useful integrators on a lakewide basis of high molecular weight, relatively involatile organochlorine pollutants such as PCRs. A search for relatively volatile organochlorine compounds by GC/MS also revealed the presence of tri- and tetrachloroethylene, and isomers of di-, tri-, tetra-, penta- and hexachlorobenzene in the body lipid of adult Herring Gulls from Lake Ontario. Analysis of pooled eggs from colonies throughout the Great Lakes in 1978 showed that pentachlorobenzene and hexachlorobenzene were ubiquitous contaminants at levels from 14–50 ng/kg and 90–350 ng/kg, respectively. Hexachlorobenzene levels were 2–3 times higher in Lake Ontario than the other lakes, whereas pentachlorobenzene was more evenly distributed geographically. Levels of 1,2,3,4-tetra-, 1,2,4,5-tetra- and 1,2,4-trichlorobenzene near the detection limit of 10–20 ng/kg were found in a few samples.     

抗生素废水的GC-MS分析与显色物质的初步确定

为确定抗生素废水中有机污染物构成和显色物质,以二氯甲烷为萃取剂,萃取废水中的有机物,经过浓缩纯化后,利用气相色谱质谱联用(GC-MS)技术对制药废水中的有机成分进行了分析鉴定,结合计算机质谱图库,定性确定了废水中60种有机污染物。其中,脂类为主要污染物成分，经对脱色后的废水进一步GC-MS分析后,初步确定油酸甲酯为此类抗生素废水的主要显色有机物。     

Organic contaminant loads into the Western Mediterranean Sea: estimate of Ebro River inputs

Annual input estimates for several organic contaminants from the Ebro River into the Northwestern Mediterranean Sea were carried out on the basis of monthly sampling from November 2002 to October 2003. Some organochlorine compounds (DDT and its degradation products, DDD and DDE, PCBs (9 congeners), HCB and gamma-HCH) were selected due to their reported occurrence in the river. Furthermore, some polar pesticides used in the Ebro Delta were also determined (atrazine, simazine, diazinon, fenitrothion and molinate). Concentrations ranged from 0.4 to 19.5 ng l(-1) for the organochlorine compounds (sum of particulate and dissolved phases) and from not detected (ND) to 170 ng l(-1) for the more polar pesticides, which were only found in the dissolved phase. The sum of PCB congeners (mean 8.9 ng l(-1)) showed the highest concentrations among the organochlorine compounds and atrazine (mean 82 ng l(-1)) among the polar pesticides. Based on the contaminant concentrations and on hydrological data, contaminant discharges into the sea were estimated amounting in total to 167 and 1,258 kg year(-1) of organochlorine compounds and polar pesticides, respectively. Furthermore, it was observed that PCBs, DDTs and HCB inputs were basically influenced by spate periods due to an increase in suspended particulate matter associated to runoff and sediment resuspension. Whereas for more water soluble contaminants, such as the agrochemicals, their seasonal use had a higher incidence in contaminant fluxes. Bulk chemical parameters such as SPM, DOC, POC, %OC, %ON and C/N ratio provided additional information on the organic matter sources. This provides a better understanding of the temporal variability of the contaminant concentrations.     

Hair analysis: another approach for the assessment of human exposure to selected persistent organochlorine pollutants

Hair analysis was used for the assessment of exposure to organochlorine pollutants in specimens from Greece, Romania and Belgium. A simple method (using 3 N HCI as incubation reagent, liquid-liquid extraction with hexane/ dichloromethane (DCM), alumina/acid silica clean-up and GC-ECD/GC-MS analysis) was used for screening of specimens. The highest organochlorine load (up to 148 ng/g hair for the sum of PCB, DDT and hexachlorocyclohexane (HCH) isomers) was found in samples from a group of Greek women with past occupational exposure to pesticides. DDTs were the main organochlorine pollutants in Greek samples (up to 70%), while in Belgian hair samples their contribution was reduced to 40%. PCB mean concentration was higher in Belgian specimens (up to 14 ng/g hair). Lindane (y-HCH) was the main HCH isomer found in the samples (up to 82% in the Greek samples). Contribution of p,p'-DDT to the sum of DDTs was higher in Greek samples and indicates recent exposure to technical DDT. Similar PCB 153/sum PCBs ratios were found for each of the three countries suggesting similar sources of pollution with PCBs (mainly dietary). Artificially coloured hair samples were found to have lower, but not statistically significant concentrations of organochlorine pollutants than the non-coloured hair.     

水解酸化-接触氧化-混凝气浮工艺处理高浓度漂染废水

本文介绍了水解酸化 -接触氧化 -混凝气浮工艺在处理高浓度漂染废水中的工程应用。结果表明 ,漂染废水经该工艺处理后CODCr去除率为 95 % ,色度去除率为 90 %。该工艺具有占地面积小 ,脱色效果好 ,处理效率高等特点 ,能广泛应用于纺织漂染废水的实际工程中     

Monitoring of organochlorine pesticides residues in green mussels (Perna viridis) from the coastal area of Thailand

The utilization of organochlorine pesticides for pest control chemical has been of great interest on residue contamination from biological organisms in the environment. Green mussel (Perna viridis) samples were monitored as bioindicators for assessment of the water quality in coastal waters along the Gulf of Thailand. Thirty-six samples were collected from 12 stations during 1997-1999 and analysed for 26 organochlorine pesticide compounds. This paper focuses on the contamination of organochlorine pesticide residues in green mussel (P. viridis) during 1997-1999. The limit of detection of all organochlorine pesticides compounds was at the range of 0.1-8.3 ng g(-1) wet weight and recovery 75-95%. The concentration of organochlorine pesticides residues in green mussel was lower than the maximum residue limit for aquatic animals as recommended by the Ministry of Public Health of Thailand. The trend of organochlorine pesticide residue contamination in this area decreased from 1989 to 1999.     

Persistent organic pollutants (POPs) in the conventional activated sludge treatment process: model predictions against experimental values

The FATE and treatibility estimator (FATE) model, developed by the United States Environmental Protection Agency was used for the prediction of the FATE of 26 persistent organic pollutants (POPs), i.e. 7 PCBs and 19 organochlorine compounds (OCs), during the conventional activated sludge treatment process applied in the waste water treatment plant (WWTP) of Thessaloniki, Greece. The removal rates predicted by the model for the primary and the secondary treatment stages were found to differ substantially from those experimentally measured. When the overall treatment was considered, the differences between measured and model predicted removals were within acceptable limits of confidence. Possible reasons that might cause deviations from experimental values were suggested to be the wastewater content in dissolved organic carbon (DOC), and/or the low concentrations of POPs in untreated wastewater.     

Organochlorine contaminants in albatrosses and petrels during migration in South Atlantic Ocean

Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed in the subcutaneous fat, liver and muscle of 100 birds belonging to eight species of Procellariiformes collected during their migration period in southern Brazil, one of the most important feeding areas for these species. Although the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p′p-DDE, organochlorine concentrations exhibited a high degree of intra-species variability. The influence of body condition during the migration period in the distribution of organochlorine contaminants was also evaluated, showing that it is a significant factor in the variation and redistribution of these compounds in the tissues of these birds. The intense use of lipid reserves associated to the contamination from organochlorine compounds could be a troubling factor for seabirds with extended breeding periods and that spend most of their lives at sea migrating long distances, such as most of Procellariiformes. Studies on contamination are necessary to improve the knowledge of the threats to these birds and their populations as well as to contribute with information about persistent organic pollutants in the South Atlantic marine environment.     

Reduction of pharmaceutically active compounds by a lagoon wetland wastewater treatment system in Southeast Louisiana

A number of pharmaceutically active compounds (PhACs) have been detected in the aquatic environment as a result of discharges of municipal wastewater. In the state of Louisiana, USA, many municipalities treat wastewater using natural systems, such as lagoons and wetlands, rather than conventional wastewater treatment technologies. Nearly all research to date has focused on the fate of PhACs in conventional treatment plants, not constructed and natural wetlands. In the wastewater treatment plant (WWTP) for Mandeville, Louisiana, USA, wastewater flows of 7600 m³ d⁻¹ are treated in a series of aeration lagoons (basins), followed by a constructed wetland and UV disinfection, before being discharged into a natural forested wetland (i.e. Bayou Chinchuba) and eventually, Lake Pontchartrain. Thirteen out of the 15 PhACs investigated were detected in the wastewater inflow to the treatment plant. Only 9 of the 13 compounds were above the detection limits at the treatment plant effluent. The concentrations of most compounds were reduced by greater than 90% within the plant, while carbamazepine and sotalol were only reduced by 51% and 82%, respectively. The percent reductions observed in the Mandeville system were greater than reduction rates reported for conventional WWTPs; perhaps due to the longer treatment time (∼30 days). Most target PhACs were not completely removed before discharge into Lake Pontchartrain, although their collective annual loading was reduced to less than 1 kg and down to ppb with significant potential for dilution in the large lake.     

Polychlorinated biphenyl congeners and organochlorine insecticides in the water column and sediments of Daya Bay, China.

Samples of sub-surface water, suspended particulate matter (SPM) and surface sediments collected from Daya Bay, China have been analysed for 12 polychlorinated biphenyl (PCB) congeners and 18 organochlorine insecticides, using gas chromatography electron capture detection. Total PCB levels varied from 91.1 to 1355.3 ng l-1 in water and from 0.85 to 27.37 ng g-1 dry weight in sediments. The levels of total organochlorine insecticides were in the range 143.3-5104.8 ng l-1 in water and 2.43-86.25 ng g-1 dry weight in sediment. None of the target compounds were detected in SPM. The levels of total hexachlorocyclohexanes in water varied from 35.5 to 1228.6 ng l-1, whilst in sediments they ranged from 0.32 to 4.16 ng g-1 dry weight. For the sum of dichlorodiphenyltrichloroethanes (DDTs), their levels were in the range 26.8-975.9 ng l-1 in water, and 0.14-20.27 ng g-1 dry weight in sediments. The distribution profiles of these contaminants in water and sediments suggest that there are a number of sources contributing to total contaminant burden in the bay, including soil runoffs, wastewater discharges, sewage outfalls and shipping activites. Ratios of DDT/(DDE + DDD) in the water and sediments indicate recent inputs of such chemicals into the day. The results, therefore, provide important information on the current contamination status of a key aquacultural area in China, and point to the need for urgent actions to stop the use of persistent agrochemicals such as DDT and lindane.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

Effect of physico-chemical pretreatment on the removal efficiency of horizontal subsurface-flow constructed wetlands

In this study, we tested the effect of a physico-chemical pretreatment on contaminant removal efficiency in two experimental horizontal subsurface-flow constructed wetlands (SSF CWs). One SSF CW was fed with settled urban wastewater, whereas the other with the same wastewater after it had undergone a physico-chemical pretreatment. The SSF CWs were operated with three different hydraulic retention times. During the experiments the effluent concentrations of COD, ammonia N and sulfate were very similar, and, therefore, the physico-chemical pretreatment did not improve the quality of the effluents. COD removal efficiency (as percentage or mass surface removal rate) was slightly greater in the SSF CW fed with pretreated wastewater. Ammonia N removal efficiency was, in general, similar in both SSF CWs and very high (80-90%). At the end of the experiments it was observed that in the SSF CW fed with settled wastewater the hydraulic conductivity decreased by a 20%.     

Reduction of pharmaceutically active compounds by a lagoon wetland wastewater treatment system in Southeast Louisiana

A number of pharmaceutically active compounds (PhACs) have been detected in the aquatic environment as a result of discharges of municipal wastewater. In the state of Louisiana, USA, many municipalities treat wastewater using natural systems, such as lagoons and wetlands, rather than conventional wastewater treatment technologies. Nearly all research to date has focused on the fate of PhACs in conventional treatment plants, not constructed and natural wetlands. In the wastewater treatment plant (WWTP) for Mandeville, Louisiana, USA, wastewater flows of 7600 m³ d⁻¹ are treated in a series of aeration lagoons (basins), followed by a constructed wetland and UV disinfection, before being discharged into a natural forested wetland (i.e. Bayou Chinchuba) and eventually, Lake Pontchartrain. Thirteen out of the 15 PhACs investigated were detected in the wastewater inflow to the treatment plant. Only 9 of the 13 compounds were above the detection limits at the treatment plant effluent. The concentrations of most compounds were reduced by greater than 90% within the plant, while carbamazepine and sotalol were only reduced by 51% and 82%, respectively. The percent reductions observed in the Mandeville system were greater than reduction rates reported for conventional WWTPs; perhaps due to the longer treatment time (30 days). Most target PhACs were not completely removed before discharge into Lake Pontchartrain, although their collective annual loading was reduced to less than 1 kg and down to ppb with significant potential for dilution in the large lake.     

Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH

This paper describes results of treatability studies of the effect of humic substances (humate, HS, at the concentration 500-5000 mg l-1) on the Fenton (Fe2+/H2O2) treatment of industrial wastewater at pH 3.5 and 7.0. Without humate, the removal of all contaminants was significantly higher at pH 3.5 than at pH 7. At pH 7.0, the removal of all compounds in the presence of HS (3000 mg l-1) was comparable to that at pH 3.5 without HS. At pH 3.5, humate had no effect on the removal of arsenic, thiocyanate and cyanide, but the removal of all organic compounds (phenol, 2,4-dimethylphenol, benzene, toluene, o-xylene, m- & p-xylene and dichloromethane) was significantly inhibited. Mechanisms of the processes are discussed. It is suggested that, in the presence of HS, acidification of the treated wastewater may not only be unnecessary but it can even hinder the degradation of organic pollutants.