Monitoring of Cr, Cu, Pb, V and Zn in polluted soils by laser induced breakdown spectroscopy (LIBS)

Laser Induced Breakdown Spectroscopy (LIBS) is a fast and multi-elemental analytical technique particularly suitable for the qualitative and quantitative analysis of heavy metals in solid samples, including environmental ones. Although LIBS is often recognised in the literature as a well-established analytical technique, results about quantitative analysis of elements in chemically complex matrices such as soils are quite contrasting. In this work, soil samples of various origins have been analyzed by LIBS and data compared to those obtained by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The emission intensities of one selected line for each of the five analytes (i.e., Cr, Cu, Pb, V, and Zn) were normalized to the background signal, and plotted as a function of the concentration values previously determined by ICP-OES. Data showed a good linearity for all calibration lines drawn, and the correlation between ICP-OES and LIBS was confirmed by the satisfactory agreement obtained between the corresponding values. Consequently, LIBS method can be used at least for metal monitoring in soils. In this respect, a simple method for the estimation of the soil pollution degree by heavy metals, based on the determination of an anthropogenic index, was proposed and determined for Cr and Zn.     

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.     

In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

A study on chemical properties of groundwater and soil in ophiolitic rocks in Firuzabad, east of Shahrood, Iran: with emphasis to heavy metal contamination

In order to assess the chemical properties of groundwater and soil in ophiolitic zone of Firuzabad, in east of Shahrood, Iran, 10 soil samples with regard to sensitive points (vicinity to mine, ophiolitic rocks, and villages) and 10 groundwater samples including nine samples from springs, and also one sample from a well in a village of the study area were taken. These samples were analyzed in laboratories using inductively coupled plasma method. The soil samples were also evaluated for grain size. The obtained results show that most of heavy and major elements were exceeding the permissible levels in soil and water samples in the study area. On the subject of soil quality, concentrations of elements Cr, Mn, Fe, Ca, Mg, Ca, Ni, and Zn are above permissible levels. Enrichment factor and index of geoaccumulation have been calculated for heavy and major elements of all soil samples. According to the obtained results, it may be argued that soil samples are contaminated in relation to the above-mentioned indices. Comparing the concentrations of elements with results of grain size analysis illustrates that the concentrations of Cr, Ni, Fe, Mg, and Co are positively correlated with sand fraction and the concentrations of Al, P, Mn, and Pb are directly proportional with clay fraction in soil samples. The study on water contamination suggests that concentrations of elements Cr, Ni, and Mg in groundwater samples of the study area are above the permissible levels. Some indices like metal index and heavy metal pollution index show that most of the water samples include heavy metal contamination.     

Elemental contamination in urban parks of Rawalpindi/Islamabad—a source identification and pollution level assessment study

The soil quality of urban parks is of vital importance as the children playing in the parks get themselves easily contaminated. A study was conducted to assess the level of elemental pollution caused by constant urbanization and industrialization, in various parks of Islamabad and Rawalpindi. The soil samples, collected from 14 urban parks of Islamabad and Rawalpindi areas, were analysed for their elemental concentrations. In each sample, 32 elements were quantified using semi-absolute k (0)-instrumental neutron activation analysis and flame atomic absorption spectrophotometry. The quality of analysis was assured by analysing the International Atomic Energy Agency (IAEA) reference material IAEA-S7 (soil). The pollution level was assessed by enrichment factor, pollution load index and our suggested indicator called "average toxic element concentration". The elemental concentrations measured in the parks of two cities were compared by t test. Four sources of different elements in the soils were identified by employing principal component analysis and cluster analysis. The results of multivariate techniques grouped all parks into four classes. The use of enrichment factor indicated the presence of Ni at slightly higher level in all parks while the pollution load index revealed that the parks of Rawalpindi were relatively more polluted as compared to that of Islamabad. The hot spot areas of elemental concentration were closely related to high traffic conditions.     

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.     

Screening of brick-kiln area soil for determination of heavy metal Pb using LIBS

Rapid measurement of heavy metals in soil is an important factor in modeling the effect of industrial pollution on agricultural soil. Conventional methods of heavy metal analysis are relatively slow in terms of measurement/analysis time and sample preparation time with the requirement of skilled manpower. Our results highlight the quantitative analysis of toxic metal lead (Pb), for the first time, in an Indian agricultural soil, in the vicinity of brick-kiln area, Phaphamau, near Allahabad, India, by using a novel technique named as Laser-induced breakdown spectroscopy (LIBS). LIBS spectra of soil has been recorded in the wavelength range from ultraviolet (UV) to infrared region (200-1,100 nm). The suitability of Pb lines for drawing the calibration curve is checked and realized, for the first time, that 220.3 nm, which is observed in the UV region of LIBS spectra, is completely interference free and best suited for the quantification of trace amount of Pb in soil instead of any other Pb lines, because it has best linear regression coefficient and smallest standard deviation of the background signal. In the present work the detection limit for Pb in soil is found to be 45 ppm. Based on the present work the concentration of Pb in agricultural soil of brick-kiln area in Phaphamau is found to be congruent with 570 ppm, which is more than the regulatory standards imposed by US Environmental Protection Agency (400 ppm) for the presence of lead in soil, therefore, it is of great concern to us.     

Effects of an Oil Spill on Soil Physico-Chemical Properties of a Spill Site in a Typic Udipsamment of the Niger Delta Basin of Nigeria

Physico-chemical analysis of soil samples at an oil spill site in a Typic Udipsamment of the Niger Delta Basin of Nigeria showed that the total hydrocarbon content of top soil layers ranged from 18.6 to 23.6 ppm in the heavy impact zone and the oil had penetrated to a depth op 8.4 m. The concentration of hydrocarbons in the medium impact zone ranged from 10.04 to 10.38 ppm while hydrocarbons were not detected in 85% of samples from the unimpacted reference zone. Heavy metal concentration measurements in the soil revealed a significant build-up (P < 0.05) of lead, copper and zinc in the heavy impact zone. Other quality parameters including electrical conductity, exchangeable cations, total nitrogen and available phosphorus in impacted soils were relatively low, while the total organic carbon was high compared with the reference site. Textural class of soil from the different depths showed a predominantly brown sand at the topsoil, loamy sand and grey coarse sand at medium depths, and grey coarse sand and greyish sandy clay at greater depths.     

激光诱导击穿光谱技术在环境领域中的应用动态

激光诱导击穿光谱技术是一种通过分析物质等离子体发射光谱而获取物质成分和含量的分析技术。近些年,该技术已经成为光谱学领域的研究热点且发展迅速,涌现出多种新的检测手段和仪器。从它的基本原理、发展历史及其在土壤、水和大气等生态环境保护领域的应用情况为基础,分析总结其优点以及所面临的问题和挑战。     

Screening level modeling of long-term impact of petroleum hydrocarbon contamination on fresh groundwater lenses in the Arabian Gulf region

The Gulf War in 1991 created an environmental catastrophe, one of the major consequences of which was setting several oil wells on fire in the Arabian Gulf area. The total oil spilled as a result of the damaged wells was about 3.5 × 10⁶ m³. Out of these, 3.3 × 10⁶ m³ of oil was recovered and exported. The rest was left behind as it was not economical to collect. The oil left behind was subject to severe weathering over the past ten years. Soil and subsurface contamination pose a serious risk to the quality of the already scarce fresh groundwater resources in the area which was subject to oil spill in the study region. This paper presents the computer modeling activities carried out towards simulating the transport of the hydrocarbon contamination of the fresh groundwater resources at a study area in the Arabian Gulf region, and predicting the contamination levels at the fresh groundwater lenses in the area in the future, should current contamination levels persist in the soil and groundwater. The modeling activities relied on both semi-analytical and numerical flow and transport models.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

Extractable copper, arsenic and antimony by EDTA solution from agricultural Chilean soils and its transfer to alfalfa plants (Medicago sativa L.)

Following our research on copper, arsenic and antimony in Chilean ecosystems, a study to understand the mobility and transport of these elements from soil to plants was carried out. So, the aim of this study, which follows on from the previous work, was to demonstrate if the total concentrations of these elements or their fractions extracted by 0.05 M EDTA pH 7 from different Chilean soils correlate with the respective total concentrations in the edible tissue of alfalfa plants collected simultaneously from 20 different sites affected or unaffected by mining activities. The highest copper fractions extracted by EDTA solutions were obtained in contaminated soils from the central region (41-69%); however the northern soils presented the highest extractable fractions of arsenic (9-34%). The antimony fraction was low in all soils (0.4-8.0%). Alfalfa plants from all contaminated sites presented high copper, arsenic and antimony concentrations (19-126 mg kg(-1), 5.7-16.3 mg kg(-1) and 0.16-1.7 mg kg(-1), respectively). Statistically significant correlations were obtained between the total contents of copper and arsenic and their respective extractable fractions in soils. Good correlations were found between elements in alfalfa plants. Correlations were also obtained between the total concentrations of three elements in soils and in alfalfa plants. However, excepting for antimony in the northern samples, higher correlation coefficients were evaluated when the extractable fractions were considered. Samples from the north region presented the highest copper transfer factor and the lowest for arsenic, in spite of the high concentration of this metalloid extracted by EDTA solution in these soils. There was not a clear trend on the transfer factor for antimony, probably due to the low content of this element in alfalfa plants and/or the low recovery obtained for this element by EDTA.     

Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Risk assessment and remediation suggestion of impacted soil by produced water associated with oil production

Produced water is water trapped in underground formations that is brought to the surface along with oil or gas production. Oilfield impacted soil is the most common environmental problem associated with oil production. The produced water associated with oil-production contaminates the soil and causes the outright death of plants, and the subsequent erosion of topsoil. Also, impacted soil serves to contaminate surface waters and shallow aquifers. This paper is intended to provide an approach for full characterization of contaminated soil by produced water, by means of analysis of both the produced water and the impacted soil using several recommended analytical techniques and then identify and assay the main constituents that cause contamination of the soil. Gialo-59 oilfield (29N, 21E), Libya, has been chosen as the case study of this work. The field has a long history of petroleum production since 1959, where about 300,000 bbl of produced water be discharged into open pit. Test samples of contaminated soil were collected from one of the disposal pits. Samples of produced water were collected from different points throughout the oil production process, and the analyses were carried out at the labs of Libyan Petroleum Institute, Tripoli, Libya. The results are compared with the local environmental limiting constituents in order to prepare for a plan of soil remediation. The results showed that the main constituents (pollutants) that impact the soil are salts and hydrocarbon compounds. Accordingly; an action of soil remediation has been proposed to remove the salts and degradation of hydrocarbons.     

Use of Sediment Quality Guidelines and pollution indicators for the assessment of heavy metal and PAH contamination in Greek surficial sea and lake sediments

Eight different surface sediment samples (K1–K8) were collected from two separate areas of Lake Koumoundourou and two samples (E1 and E2) from one area of Elefsis Bay, Athens, Greece. The level of pollution attributed to heavy metals was evaluated using several pollution indicators. Degree of Contamination, Modified Contamination Degree and Geoaccumulation Indexes were applied in order to determine and assess the anthropogenic contribution of the selected six elements (Cr, Ni, Cu, Zn, As and Pb). Moreover, the adverse effects of the sediments to aquatic organisms, from both heavy metals and polycyclic aromatic hydrocarbons (PAHs), were determined by using Sediment Quality Guidelines. The results indicated that Lake Koumoundourou is contaminated with heavy metals in a moderate degree and almost 50 % of the sediments are associated with frequent observation of adverse effects, when it comes to Ni and occasional observation of adverse effects, when it comes to Cu, Zn and Pb. As far as PAHs are concerned, around 60 % of the samples can be occasionally associated to toxic biological effects according to the effect-range classification for phenanthrene, benzo(a)anthracene, chrysene and pyrene. Finally, samples taken from the north side of the lake are more contaminated with PAHs than the ones taken from the east side probably due to the existence of the water barrier which acts as a reservoir of PAHs.     

Element content of propolis collected from different areas of South Spain

The aim of this work is to determine the content of essential and toxic elements in 25 raw propolis samples, when considering pollution agents and geographical and botanical factors. The microwave-assisted digestion was the most reliable and accurate method for determination of inorganic elements in propolis samples. The results were obtained using certified reference materials in a good agreement with certified values. Inductively coupled plasma atomic emission spectroscopy was used for the determination of 23 macro- and microelements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, and Zn). A Mercury analyzer was also utilized for the detection of the total Hg. Among the analyzed metals, Ca, K, Mg, Zn, Si, S, Fe, Al, P, and Na were found to be the most predominant. Heavy metals (As, Cd, Hg, and Pb) were determined in minimal concentration, and Pb was the highest mean contained toxic (<3.80 mg/kg), without influence on provisional tolerable weekly intake values. The method can be applied for routine analysis and quality and environmental pollution controls of toxic elements in propolis samples. The results obtained indicate no pollution of the collection areas and naturally high concentration of Al (460?±?62.2 mg/kg).     

Restoration of taxonomic and functional genes after bioaugmentation of petroleum contaminated soil

Soil microbial ecosystems are responsive to environmental changes that underpin the biological functions of the soil. The present study was conducted to profile variations in the microbial ecological system of remediated soil (R) and petroleum contaminated soil (P) based on comparisons with soil that had not been contaminated (N), using a cloning library of taxonomic genes (16S rRNA gene for bacteria and 18S rRNA gene for eukaryotes) and functional genes (nifH, amoA and narG). The results showed that N and R had a similar distribution in both the taxonomic genes and functional genes for bacteria and eukaryotes, which were dominated by Proteobacteria and Arthropoda, respectively. Phylogenetic analysis based on the nifH gene showed that the sequences from the three soils were clustered into six taxonomic groups, Actinobacteridae, and Alpha-, Beta-, Gamma- and Delta-proteobacteria, as well as an unclassified group. Evaluation of the amoA gene revealed that all sequences derived from the three samples belonged to Betaproteobacteria. The R and N soil had similar Shannon-Wiener diversity index (H') values, both of which were significantly higher than that of the P soil. The most abundant bacterial phylotype identified in the N and R soils were the same and were related to an uncultured bacterial clone (GAN-SB17, FN423475). None of the narG genes were found in the P soil. Similar results in terms of distribution, composition and the related index were obtained for nifH and amoA. These parameters may comprise a biological ecology index that may be applied to aid the design, implementation and evaluation of soil bioremediation.     

一种便携式荧光测油仪在海上溢油应急监测中的适用性研究

研究了一种便携式荧光测油仪在海上溢油应急监测中的适用性,并与现行仲裁标准方法进行比较分析。研究表明:该便携式荧光测油仪测定海水中油类样品仅需100 mL水样,平均每个样品所需的前处理时间约340 s,方法检出限为0.003 mg/L,测定下限为0.012 mg/L。测定用标准物质配制的不同浓度海水样品,相对标准偏差为0.08%~0.87%,测定标准样品的相对误差为0.49%~4.50%,实际样品加标回收率为90%~107%。对标准物质配制的海水样品进行检测,与现行仲裁标准方法在0.05水平下无显著性差异。在渤海中部海上监测中,连续6 d测定不同标准样品的相对标准偏差为0.26%~0.83%。研究结果表明,该便携式荧光测油仪适用于现场对油类的定量分析和水质评价。     

Metal Pollution in the Environment of Minas Gerais State – Brazil

Intense mining activities in Minas Gerais State – Brazil brings out tons of waste to the environment. Considerable concentrations of toxic elements penetrate the soil, ground waters and rivers. This endangers the environment quality not only in the surrounding areas but also in ichthyofauna and in more distant areas of cattle raising and agricultural activities. After seasonal floods, veterinary clinic studies have shown that most animals raised in this region are affected by symptomatologic nervous diseases, still not clearly diagnosed, which suggests intoxication. These pathologies are mostly noted after floods. Instrumental Neutron Activation Analysis was applied to determine Al, As, Au, Ba, Br, Ca, Cl, Co, Cr, Cs, Cu, Fe, Hg, K, La, Mg, Mn, Na, Nd, Rb, Sb, Sc, Sm, Th and Zn in environmental samples. The obtained results show that the water and sediment contaminated with heavy metals and toxic elements from the Das Velhas River upstream basin, the mining region, carry contamination to the ichthyofauna and farming region within a distance of approximately 400 km.     

广西一个典型矿业镇环境中重金属污染分析

广西河池市是我国重要的有色金属基地.以该市一个典型的矿业镇作为研究对象,采集了该镇周围23个旱地土壤样品,并在镇里布设两个大气采样点采集了可吸入颗粒物(PM10)样品,运用ICP-MS分析了样品中20种金属元素的含量,采用地积指数法判定旱地土壤和可吸入颗粒物中污染元素及来源.结果表明,这些与人们生活密切的环境介质(旱地土,可吸入颗粒物)均受到了多种重金属元素的复合污染,其共同的污染元素有Cd、As、Sb、Pb、Xn、Cu,而其中致癌元素Cd和As污染最为突出.大气可吸入颗粒物与旱地土壤中各污染元素的污染强度排序相同,均为Cd＞As＞Sb＞Pb＞Zn＞Cu.经过现场调查和识别,污染源主要来自当地开放性运矿产生的扬尘所致.因此加强该地区矿石运输管理是保护该地区耕地和人群健康的需要.