Monitoring of toxic elements present in sludge of industrial waste using CF-LIBS

Industrial waste is one of the main causes of environmental pollution. Laser-induced breakdown spectroscopy (LIBS) was applied to detect the toxic metals in the sludge of industrial waste water. Sludge on filter paper was obtained after filtering the collected waste water samples from different sections of a water treatment plant situated in an industrial area of Kanpur City. The LIBS spectra of the sludge samples were recorded in the spectral range of 200 to 500 nm by focusing the laser light on sludge. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique was used for the quantitative measurement of toxic elements such as Cr and Pb present in the sample. We also used the traditional calibration curve approach to quantify these elements. The results obtained from CF-LIBS are in good agreement with the results from the calibration curve approach. Thus, our results demonstrate that CF-LIBS is an appropriate technique for quantitative analysis where reference/standard samples are not available to make the calibration curve. The results of the present experiment are alarming to the people living nearby areas of industrial activities, as the concentrations of toxic elements are quite high compared to the admissible limits of these substances.     

燃煤电厂周边大气重金属污染特征及来源解析

为探究燃煤电厂周边大气环境中重金属的污染特征与来源,对广东某山区燃煤电厂周边地区环境和污染源的重金属进行测定,分析其污染特征,采用因子分析法和Pb同位素示踪法对环境中的重金属进行来源解析。结果表明,研究区域室内积尘中重金属浓度水平明显高于土壤重金属,污染空间分布与当地气象条件相关。环境空气TSP中重金属主要来自2个污染源,Cd、Pb、As主要来自电厂燃煤,Ca、Mn、Al、Mg主要来自土壤扬尘。TSP、降尘、积尘样品所含的Pb均与电厂采集的煤、炉渣、粉煤灰样品所含的Pb具有同源性,与其他污染源同源性不明显,说明研究区域大气中Pb污染主要来自电厂燃烧所排放的烟尘,其他污染源影响不大。     

The health hazards of potentially toxic metals in the daily diets of adults and children from a mining and smelting region (Hezhang County) in southwestern China

Toxic metals accumulated in the human body are predominantly absorbed by the digestive tract in non-occupationally exposed populations. In the current study, we collected plowed soil samples, and investigated the varied food compositions in a mining and smelting area in southwestern China, to measure the concentrations of ten potentially toxic metals—As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sr, and Zn. We collected information on the daily intakes of these metals to assess the health risks associated with their exposure among children and adults. The urine concentrations of the metals were also measured to obtain data on the amounts present in the body. The results showed that the hazard indexes (HIs) of As, Ba, Cd, Cr, Ni, Pb, and Sr were all larger than 1, for both adults and children; the Zn and Cu values were comparatively higher in children. The intake of staple foods of the region posed the greatest health risk, while drinking water only posed risks clearly associated with As exposure. The urine samples of local residents contained larger amounts of As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn, confirming the hazards in the health risk assessment. Obvious differences in the urine metal concentrations between men and women were confirmed. In conclusion, higher concentrations of metals in the surface soil and rain water were the predominant cause of elevated exposure through home-grown crops and produce to accumulate in local residents’ bodies.     

Copper and Zinc in a paddy field and their potential ecological impacts affected by wastewater from a lead/zinc mine, P. R. China

As well known, at normal levels, copper and zinc are essential micronutrients for plants, animals, and humans. However, excessive Cu and Zn are toxic and disturb a wide range of biochemical and physiological processes. Using Atomic Absorption Spectrophotometer (AAS; Perkin-Elmer 3030, USA), soil and rice plant (Oryza sativa L.) samples collected from a paddy field in Lechang lead-zinc mine area, Guangdong Province, China were analyzed and their potential ecological impacts to local human and livestock were evaluated. The results showed that the paddy soils were contaminated with Cu and Zn. Both metals in soils had low bio-available fractions for paddy plants, animal and human by three chemically analytical techniques. Generally, were concentrations of copper and zinc root > straw > stalk > grain with hull > grain without hull (i.e. unpolished rice) and in the normal ranges indicating no ecological risk for local livestock and residents. All positive correlation coefficients, however, between heavy metals in rice plant and total, exchangeable (step 1 in Tessier's method established in 1979) and DTPA-extractable fractions in soils were found in this study indicating that elevated heavy metal in soils would increase long-term exposition and possible consequence of ecological hazard through food chains.     

Topsoil and Housedust Metal Concentrations in the Vicinity of a Lead Battery Manufacturing Plant

The aim of the study was to determine the extent of heavy metal pollution in the vicinity of a lead battery manufacturing plant in the Czech Republic, both in the general environment and within homes. Topsoils (0–5 cm) were sampled from 100 sites along 4 transects which crossed the battery factory, the town centre and outlying rural areas. Housedust samples were collected from 15 plant-workers' homes and 15 non plant-workers' homes located at various distances from the factory. Samples were analysed for levels of Pb, Zn, Cd, Cu, As and Sb, using ICP-AES. Soil concentrations of Pb, Cd, As and Sb peaked at the perimeter fence of the battery factory with Pb levels of up to 12 650 g g> ^-1. Concentrations of these metals decreased exponentially within 500 m of the plant. Whilst the battery factory does appear to be a source of all the metals with the exception of Zn, emissions do not appear to be transported to any great extent over distances of more than 0.5 km. Topsoil and housedust concentrations of Pb, Zn, Cd, Cu, As and Sb in the general Mlada Boleslav area do not appear to be significantly different from those recorded in a large scale survey of urban soils in the United Kingdom. A comparison of housedust Pb concentrations in homes of plant workers and non-plant workers suggests that there may be a small input of Pb into the home environment by battery plant employees.     

Biomonitoring of Lead, Zinc, and Cadmium in Streams Draining Lead-Mining and Non-Mining Areas, Southeast Missouri, USA

We evaluated exposure of aquatic biota to lead (Pb), zinc (Zn), and cadmium (Cd) in streams draining a Pb-mining district in southeast Missouri. Samples of plant biomass (detritus, periphyton, and filamentous algae), invertebrates (snails, crayfish, and riffle benthos), and two taxa of fish were collected from seven sites closest to mining areas (mining sites), four sites further downstream from mining (downstream sites), and eight reference sites in fall 2001. Samples of plant biomass from mining sites had highest metal concentrations, with means 10- to 60-times greater than those for reference sites. Mean metal concentrations in over 90% of samples of plant biomass from mining sites were significantly greater than those from reference sites. Mean concentrations of Pb, Zn, and Cd in most invertebrate samples from mining sites, and mean Pb concentrations in most fish samples from mining sites, were also significantly greater than those from reference sites. Concentrations of all three metals were lower in samples from downstream sites, but several samples of plant biomass from downstream sites had metal concentrations significantly greater than those from reference sites. Analysis of supplemental samples collected in the fall of 2002, a year of above-average stream discharge, had lower Pb concentrations and higher Cd concentrations than samples collected in 2001, near the end of a multi-year drought. Concentrations of Pb measured in fish and invertebrates collected from mining sites during 2001 and 2002 were similar to those measured at nearby sites in the 1970s, during the early years of mining in the Viburnum Trend. Results of this study demonstrate that long-term Pb mining activity in southeast Missouri has resulted in significantly elevated concentrations of Pb, Cd, and Zn in biota of receiving streams, compared to biota of similar streams without direct influence of mining. Our results also demonstrate that metal exposure in the study area differed significantly among sample types, habitats, and years, and that these factors should be carefully considered in the design of biomonitoring studies.     

Leaching Characteristics of Fly Ash from Thermal Power Plants of Soma and Tunçbilek, Turkey

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions but also with the disposal of ash residues. In particular, use of low quality coal with high ash content results in huge quantities of fly ash to be disposed of. The main problem related to fly ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly ash contacts water. In this study, fly ash samples obtained from thermal power plants, namely Soma and Tunçbilek, located at the west part of Turkey, were subjected to toxicity tests such as European Committee for standardization (CEN) and toxicity characteristic leaching (TCLP) procedures of the U.S. Environmental Protection Agency (U.S. EPA). The geochemical composition of the tested ash samples from the power plant show variations depending on the coal burned in the plants. Furthermore, the CEN and TCLP extraction results showed variations such that the ash samples were classified as `toxic waste' based on TCLP result whereas they were classified as `non-toxic' wastes based on CEN results, indicating test results are pH dependent.     

Soil Contamination Due to Heavy Metals from an Industrial Area of Surat, Gujarat, Western India

The pollution of soil is a source of danger to the health of people, even to those living in cities. The anthropogenic pollution caused by heavy industries enters plants then goes through the food chain and ultimately endangers human health. In the context, the knowledge of the regional variability, the background values and anthropogenic vs. natural origin of potentially harmful elements in soils is of critical importance to assess human impact. The present study was undertaken on soil contamination in Surat, Gujarat (India). The aims of the study were: i) to determine extent and distribution of heavy metals (Ba, Cu, Cr, Co, Ni, Sr, V and Zn) ii) to find out the large scale variability, iii) to delineate the source as geogenic or anthropogenic based on the distribution maps and correlation of metals in soils. Soil samples were collected from the industrial area of Surat from top 10 cm layer of the soil. These samples were analysed for heavy metals by using Philips PW 2440 X-ray fluorescence spectrometer. The data reveal that soils in the area are significantly contaminated, showing higher levels of toxic elements than normal distribution. The heavy metal loads of the soils in the study area are 471.7 mg/kg for Ba, 137.5 mg/kg for Cu, 305.2 mg/kg for Cr, 51.3 mg/kg for Co, 79.0 mg/kg for Ni, 317.9 mg/kg for Sr, 380.6 mg/kg for V and 139.0 mg/kg for Zn. The higher concentrations of these toxic metals in soils need to be monitored regularly for heavy metal enrichment.     

Trace metals solubility in rainwater: evaluation of rainwater quality at a watershed area, Istanbul

In this study, 79 bulk precipitation samples were collected at two sampling sites near Büyükçekmece Lake, one of the important drinking water sources of Istanbul, for the period of October 2001 to July 2002. The study comprised the determination of trace and toxic metals concentrations in rain water. The concentrations of the metals in this study were found to be higher than those reported by other researchers around the world. The solubility of toxic metals was found in the order of Cd > Cu > V > Zn > Ni > Pb > Cr. Solubility of metals under acidic conditions (pH < 5.5) was approximately five times higher than those under neutral conditions with Cd as the most soluble metal (50% soluble). Statistical evaluations including seasonal variations, crustal enrichment factors, and correlation matrix were discussed to identify the possible sources of these pollutants. The study revealed that anthropogenic elements were highly enriched especially for Cd > Cu > Pb which were found to be highly enriched. Significant portion of Cu and Pb could be increased by the effect of local sources like cement industry in the area; however, the rest of the investigated trace metals could be brought to the sampling site by long-range transport to the Büyükçekmece Lake watershed area.     

Honeybees (<Emphasis Type="Italic">Apis mellifera</Emphasis>) as a biological barrier for contamination of honey by environmental toxic metals

The aim of the study was to investigate the transfer of toxic metals from honeybee workers (Apis mellifera L.) to bee honey in relation to the ecological state of the environment. The materials of the study consisted of samples of honeybee bodies and varietal honeys taken from the same apiary located in three areas: R1—urbanized (16), R2—ecologically clean (16) and R3—industrialized (15) of south-eastern Poland. The contents of 14 elements in all tested samples, including toxic metals (Cd, Pb, Hg, Al, Ni, Tl) as well as bioelements (K, Mg, Ca, Mn, Fe, Zn, Cu, Se), were analysed by the ICP-OES method with prior microwave mineralization. The concentrations of the majority of the studied elements, excluding aluminum and lead, were significantly higher in bee bodies than in honey samples (P?<?0.05). The pollution of bee bodies by toxic metals was dependent on the environmental cleanliness, and the most pollution was observed in the industrialized area. The bee body was the most effective barrier for Cd and Tl transfer to the honey, while the level of Ni was similar in both tested materials. The Al concentration was significantly higher in honey than bee bodies (14.81?±?24.69 and 6.51?±?5.83 mg kg^?1, respectively), which suggests the possibility of secondary contamination of honey. The greatest sensitivity to heavy metal pollution was observed in honeydew honey compared to nectar honeys (P?<?0.05). It was proved for the first time that bees work as biofilters for toxic metals and prevent honey contamination.     

Risks associated with the mining of Pb–Zn minerals in some parts of the Southern Benue trough,Nigeria

The environmental effects of the mining of lead–zinc mineralization in Enyigba area, Southern Benue trough were examined. The samples used for this study were obtained from abandoned mine sites, mine tailings, streams, hand-dug wells, mine pond and borehole. Collected samples were subjected to X-ray fluorescence, X-ray diffraction analyses, atomic absorption spectrometry and permeability tests. These were done using standard laboratory equipment and procedures. The concentrations of heavy metals present in analysed water samples fall below the world health organizations’ (WHO) acceptable limits. Conversely, the soil, mine tailings and stream sediments indicate appreciable pollution level by some potential toxic metals (PTMs). Consequently, the habitual use of these soils for construction purpose by inhabitants has possible health hazards. The shaly lithology underlying the area is increasingly affected by weathering and lateritization, thus improving its permeability and the easiness with which PTMs can be conducted to the water table by leachate. Regular monitoring assessment is recommended to ensure adherence of miners operating in the area to existing environmental laws.     

Fuzzy logic modeling of bioaccumulation pattern of metals in coastal biota of Ondo State,Nigeria

The accumulation patterns of ten metals in tissues of plant, Eichornia crassipes, and fishes, Hydrocynus forskahlii and Oreochromis mossambicus, were modeled with simple fuzzy classification (SFC) to assess toxic effects of anthropogenic activities on the coastal biota. The plant sample was separated into root, stem, and leaves and the fishes into bones, internal tissues, and muscles. They were analyzed for As, Cd, Cr, Cu, Ni, Pb, V, Fe, Mn, and Zn after wet oxidation of their dried samples. The results were converted into membership functions of five accumulation classes and aggregated with SFC. The classification results showed that there was no metal accumulation in the plant parts while the fishes were classified into low accumulation category. The internal tissues of the fishes had higher metal accumulation than the other parts. Generally, Fe and Mn had highest concentrations in the biota but are natural to the area and may not constitute significant risk. Cr had the highest transfer and accumulation from the coastal water into the aquatic lives and may be indicative of risk prone system being a toxic metal. Metal contaminations in the zone had not significantly accumulated in the biota making them less prone to risk associated with metal accumulation.     

Effects of leachant temperature and pH on leachability of metals from fly ash. A case study: Can thermal power plant, province of Canakkale, Turkey

Lignite powered electric generation plants result in increasing environmental problems associated with gaseous emissions and the disposal of ash residues. Especially, low quality coals with high ash content cause enormous quantities of both gaseous and solid fly ash emissions. The main problem is related to the disposal of fly ash, which, in many cases, contains heavy metals. It is known that toxic trace metals may leach when fly ash is in contact with water. In this study, fly ash samples obtained from the thermal power plant in the town of Can in Turkey were investigated for leachability of metals under different acidic and temperature conditions. The experimental results show that a decrease in pH of the leachant favors the extraction of metal ions from fly ash. A significant increase in the extraction of arsenic, cadmium, chromium, zinc, lead, mercury, and selenium ions from the ash is attributed to the instability of the mineral phases. These heavy metals concentrations increase with respect to increasing acidic conditions and temperature. Peak concentrations, in general, were found at around 30°C.     

Monitoring and assessment of toxic metals in Gulf War oil spill contaminated soil using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was applied for the detection of toxic metals in oil spill contaminated soil (OSCS). The OSCS samples were collected from Khursania Saudi Arabia along the coast of Persian Gulf exposed to oil spills in 1991 Gulf war. Environmentally important elements like Aluminum Magnesium, Calcium, Chromium, Titanium, Strontium, Iron, Barium, Sodium, potassium, Zirconium and Vanadium from the contaminated soil have been detected. Optimal experimental conditions for analysis were investigated. The LIBS system was calibrated using standard samples containing these trace elements. The results obtained using Laser-Induced Breakdown Spectroscopy (LIBS) were compared with the results obtained using Inductively Coupled Plasma Emission Spectroscopy (ICP). The concentrations of some elements (Ba and Cr) were found higher than permissible safe limits. Health risks associated with exposure to such toxic elements are also discussed.     

Accumulation of metals in the soil of an overland flow wastewater treatment system

Accumulation of Co, Cu, Cr, Mo, Ni, Pb and Zn was evaluated in a soil profile of an overland flow system used for the post-treatment of urban wastewater. A pilot version of the overland flow system received urban wastewater from five up-flow anaerobic filters filled with bamboo (Bambusa tuldoides) rings. The anaerobic effluent was applied as feed over 18 months at rates varying from 7 to 28 L min(-1), to a vegetated slope length covered with Tifton 85 (Cynodon) sp. grass. Soil and plant samples were collected in triplicate from the top to the bottom of the slope. In addition, the soils were sampled at the depths 0-20 and 20-40 cm. The metal concentrations found in the overall system were compared to those obtained in a control area located at the beginning of the slope onto which nothing was applied. A month of monitoring the urban wastewater of Limeira City (S?o Paulo State, Brazil) showed a drastic change in metals concentration due to the irregular discharge of industrial waste. This irregular discharge introduces Cr, Cu, Ni, Pb and Zn into the system used to treat domestic wastewater. The mass balance indicates the accumulation of metals in the soil and the translocation to the plants; also that they could be evapotranspirated, percolated and discharged.     

Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.     

典型铝塑厂周边土壤重金属分布特征与健康风险评价

为探究铝塑园区周边土壤重金属污染情况,选取山东省某城市塑料开发区为研究区,按照分层采样方式获取到80个土壤样品,分别测定土壤中As、Cd、Hg、Cr、Cu、Ni、Pb、Zn含量,运用统计分析法探讨土壤重金属等的分布特征和来源,并利用健康风险评价模型确定了土壤重金属对周边居民的健康风险。结果表明:As、Cd、Hg、Cr、Cu、Ni、Pb和Zn均超出山东省土壤背景值,其中Cd、Hg、Cu和Pb分别超出背景值48. 15%、106. 90%、62. 04%和39. 96%,表明土壤中存在一定程度的重金属积累,在周边140～210 m处最为严重,且受人类活动影响强烈,与风向关系不大;土壤重金属垂直分布特征大致呈现随着深度的增加不断增加,在20 cm深度附近达到最高值,其后不断降低并趋于平稳,Cd、Hg、Cu、Pb和Zn变异幅度大,受到人为干扰较大,As、Cr和Ni主要受成土母质控制,属于自然来源,变动幅度较小;研究区内8种元素不存在非致癌风险,Cr、As、Ni和Cd产生的致癌风险处在可接受范围内,但存在的潜在致癌风险应引起足够的重视。     

Assessment of the impact of petroleum and petrochemical industries to the surrounding areas in Malaysia using mosses as bioindicator supported by multivariate analysis

Biomonitoring of multi-element atmospheric deposition using terrestrial moss is a well-established technique in Europe. Although the technique is widely known, there were very limited records of using this technique to study atmospheric air pollution in Malaysia. In this present study, the deposition of 11 trace metals surrounding the main petroleum refinery plant in Kerteh Terengganu (eastern part of peninsular Malaysia) has been evaluated using two local moss species, namely Hypnum plumaeforme and Taxithelium instratum as bioindicators. The study was also done by means of observing whether these metals are attributed to work related to oil exploration in this area. The moss samples have been collected at 30 sampling stations in the vicinity of the petrochemical industrial area covering up to 15 km to the south, north, and west in radius. The contents of heavy metal in moss samples were analyzed by energy dispersive x-ray fluorescence technique. Distribution of heavy metal content in all mosses is portrayed using Surfer software. Areas of the highest level of contaminations are highlighted. The results obtained using the principal components analysis revealed that the elements can be grouped into three different components that indirectly reflected three different sources namely anthropogenic factor, vegetation factor, and natural sources (soil dust or substrate) factor. Heavy metals deposited mostly in the distance after 9 km onward to the western part (the average direction of wind blow). V, Cr, Cu, and Hg are believed to have originated from local petrochemical-based industries operated around petroleum industrial area.     

Deposition fluxes of PCDD/Fs in the area surrounding a steel plant in northwest Italy

The paper aims at investigating the contribution of a steel plant located in a rural area in northwestern Italy (700,000 tons of steel/year) to the deposition fluxes of Polychorinated Dibenzo-p-dioxins and Polychorinated dibenzofurans (PCDD/PCDFs) at local level through the analysis of sampling data, literature data, and air dispersion model (AERMOD)output data. Total measured deposition fluxes of PCDD/PCDFs in three monitoring stations were consistent with other studies carried out in Italy in urban and suburban areas and in rural European areas; while these were lower than those measured in other European urban/suburban areas or in sites influenced by industrial sources. Furthermore, the measured fluxes were also compared with the pattern of PCDD/Fs in ambient air sampled at the same sites in a previous study. This comparison showed a similarity between air concentration and deposition patterns of the samples collected at the three monitoring stations and a clear distinction of these from the source. The study was completed with AERMOD simulations, conducted with a mass mean particle diameter of 0.5 μm, according to the particle size distribution of the samples collected at the source. AERMOD calculated deposition fluxes of two to three orders of magnitude lower than those measured in two monitoring points; while in the most distant monitoring station, the deposition fluxes were too low to be calculated by the model. The simulations confirmed that the most distant monitoring station was not subject to emissions from the steel plant. The analysis highlighted the limited influence of the source in the local PCDD/F deposition fluxes.     

Stormwater toxicity in Chollas Creek and San Diego Bay,California

Stormwater discharges from Chollas Creek, a tributary of San Diego Bay, have been shown to be toxic to aquatic life. The primary objective of this study was to provide the linkage between in-channel measurements and potential impairments in the receiving waters of San Diego Bay. This study addressed this objective within the context of four questions: (1) How much area in San Diego Bay is affected by the discharge plume from Chollas Creek during wet-weather conditions?; (2) How much of the wet-weather discharge plume is toxic to marine aquatic life?; (3) How toxic is this area within the wet-weather discharge plume?; and (4) What are the constituent(s) responsible for the observed toxicity in the wet-weather plume? The stormwater plume emanating from Chollas Creek was dynamic, covering areas up to 2.25 km2. Approximately half of the plume was estimated to be toxic to marine life, based upon the results of purple sea urchin (Strongylocentroutus purpuratus) fertilization tests. The area nearest the creek mouth was the most toxic (NOEC = 3 to 12% plume sample), and the toxicity decreased with distance from the creek mouth. The toxicity of plume samples was directly proportional to the magnitude of plume mixing and dilution until, once outside the plume margin, no toxicity was observed. Trace metals, most likely zinc, were responsible for the observed plume toxicity based upon toxicity identification evaluations (TIEs). Zinc was also the constituent identified from in-channel samples of Chollas Creek stormwater using TIEs on the storms sampled in this study, and in storms sampled during the previous storm season.