Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Trace element atmospheric pollution in South Albania studied by the moss technique and inductively coupled plasma–atomic emission spectrometry

Monitoring hazardous air pollutants is needed for understanding their spatial and temporal distribution and ultimately to minimize their harmful effects. For the first time, the moss biomonitoring technique has been applied to air pollution monitoring in South Albania. Moss samples were collected during the period of September–October 2010, and were analyzed for total concentration of the elements Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V, and Zn by inductively coupled plasma–atomic emission spectrometry. Geographical distribution maps of the elements over the sampled territory were constructed using geographic information systems technology. Multivariate statistical analysis was applied to distinguish elements mainly of anthropogenic origin from those predominantly originating from natural sources. Four factors were identified: Factor 1 reflects wind-blown mineral particles or local emissions from industry (Al, As, Ba, Ca, Cr, Cu, Fe, Mn, Ni, V, Zn); Factor 2 is related to long-range atmospheric transport of elements or local emissions from industry (Cd, Pb); Factor 3 (Na, Mg) and Factor 4 (K) reflect the natural origin of elements as crustal, marine, and vegetation components.     

Study on particulate and metallic elements variation at daytime and nighttime period in urban atmosphere

Daily PM_2.5, PM_2.5–10 and TSP have been collected by Universal and PS‐1 sampler simultaneously at a site within Taichung between February and March 1999. The filters were analyzed by atomic absorption spectrophotometry for the elemental analysis of Ca, Fe, Mn, Pb, Cu, Zn and Cr. In general, the concentration of these metallic elements are higher in fine particles than in coarse particles. On average, PM₁₀ accounted for 67% of the TSP at daytime, while at nighttime PM₁₀ accounted for only 44% of the TSP. For PM_2.5, PM₂._5–10 and TSP concentrations, there were no significant differences between day and night period. The averaged concentrations of metallic elements in PM_2.5 at daytime were all higher than that at nighttime. Ca, Fe and Zn have large and variable PM_2.5 concentrations at both daytime and nighttime. For the daytime Zn and Pb account for the largest portion of the heavy metal elements. For the nighttime, Zn and Cr make the largest portion of the heavy metal elements. The concentrations of Mn were higher on fine particulates. The trace metals Cu and Cr in Taichung are probably due to particulates emitted by Taichung Fire Power Plants transported into the sampling area by the prevailing northwesterly wind.     

Trace elements in particulate matter of ambient air at petroleum filling stations

Size segregated suspended particulate matter (PM_2.5 and PM_10-2.5) in air at four major petroleum-filling stations in Ile-Ife, Nigeria, were monitored using double staged “Gent” stacked samplers to assess variations in mass loads and elemental concentrations of 25 elements. Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, Cs, Ta, W, and Pb were determined in both fractions by external ion beam proton-induced X-ray emission technique. Enrichment factors and pollution indices were calculated and results revealed that most elements were anthropogenic in both fractions with concentrations exceeding the World Health Organization guideline standards.     

Ambient air particulates-bound metallic elements sources identifications during winter and summer at a Science Park

The ambient air particulates pollutants of total suspended particulates (TSP) and PM_2.5 were collected by using PS-1 and Wilbur PM_2.5 sampler, simultaneously during the year of 2015–2017 at a photoelectric factory in Science Park of central Taiwan. And those of the ambient air atmospheric metallic elements (Cr, Mn, Ni, Cu, Zn, Pb) concentrations which attached on the TSP and PM_2.5 were analyzed by using inductively coupled plasma optical emission spectrometer. In addition, identifying anthropogenic and natural pollutants sources were conducted by using the enrichment factor (EF) and principal component analysis (PCA) methods. The results indicated that the average TSP and PM_2.5 concentrations were ranked highest in winter season, while summer season was ranked lowest during the year of 2015–2016. In addition, the average highest metallic element concentrations were occurred in winter season for both TSP and PM_2.5 during the year of 2015–2016, while the average lowest metallic elements concentrations in TSP and PM_2.5 were also occurred in winter season during the year of 2016–2017. Moreover, the EF analysis results showed that the metallic element Zn came from anthropogenic emission source. As for metallic element Mn, the results showed that metallic element Mn was mainly attributed to natural emission in this study. Finally, the PCA results showed that metallic elements Cr, Zn and Pb were the dominant emissions metallic elements in this study. As for PM_2.5, the results showed that the metallic elements Cr, Cu and Pb were the dominant emissions metallic elements at this HPB sampling site.

     

Scalp hair metal analysis in the assessment of the occupational exposure of arc welders

Eleven metals (Ca, Mg, Fe, Zn, Cu, Mn, Cd, Co, Cr, Ni and Pb) were estimated in hair samples of metal arc welders and a control group with the same socioeconomic background. Nitric acid–perchloric acid wet digestion procedure was adopted for the estimation of endogenous metal contents by ICP-AE technique. The study exhibited the following increasing order of the metal concentrations: Cd??1, dry weight, respectively. On average, the levels of Mn, Ni, Pb and Fe were found to be 1.5–2.4 times higher in the hair of welders compared with controls. Besides age and exposure which were strongly correlated, Cu–Mg, Mn–Mg, Ca–Co and Cd–Zn also showed significantly positive correlations. The identification of metal sources, done by cluster and principal component analyses, revealed four factors: age and exposure; Cu, Mg, Mn and Fe; Ca and Co; Cd, Zn, Ni and Pb. High levels of Fe were found to have a depleting impact on Co levels. The arc welders were feared to accumulate heavy metals in their bodies due to long-term endogenous exposure.     

Improved characterisation of inorganic components in airborne particulate matter

We set up a microanalytical procedure for non-volatile ions by ion chromatography (IC) and for elements by energy-dispersive X-ray fluorescence (ED-XRF) and inductively coupled plasma optical emission spectroscopy (ICP-OES). We analysed NO₃, SO₄, NH₄, Na, Mg, Ca, Fe, S, Zn, As, Cd, Cu, Mn, Ni, Pb, Sb, Se, Ti, and V. The use of complementary techniques yields reliable data for both trace and crustal elements, overcoming the analytical restrictions characteristic of the individual techniques. Some elements determined by two or by all three techniques can be used as data quality markers. The application of the procedure to a short PM_2.5 monitoring campaign is also described, aimed to the identification of fireworks tracers.     

Trace element contents in fine particulate matter (PM<Subscript>2.5</Subscript>) in urban school microenvironments near a contaminated beach with mine tailings,Chañaral,Chile

Air quality in schools is an important public health issue because children spend a considerable part of their daily life in classrooms. Particulate size and chemical composition has been associated with negative health effects. We studied levels of trace element concentrations in fine particulate matter (PM_2.5) in indoor versus outdoor school settings from six schools in Chañaral, a coastal city with a beach severely polluted with mine tailings. Concentrations of trace elements were measured on two consecutive days during the summer and winter of 2012 and 2013 and determined using X-ray fluorescence. Source apportionment and element enrichment were measured using principal components analysis and enrichment factors. Trace elements were higher in indoor school spaces, especially in classrooms compared with outdoor environments. The most abundant elements were Na, Cl, S, Ca, Fe, K, Mn, Ti, and Si, associated with earth’s crust. Conversely, an extremely high enrichment factor was determined for Cu, Zn, Ni and Cr; heavy metals associated with systemic and carcinogenic risk effects, whose probably origin sources are industrial and mining activities. These results suggest that the main source of trace elements in PM_2.5 from these school microenvironments is a mixture of dust contaminated with mine tailings and marine aerosols. Policymakers should prioritize environmental management changes to minimize further environmental damage and its direct impact on the health of children exposed.     

Toxicity evaluation of a complex metal mixture to the softshell clam Mya arenaria

Adults of the softshell clam Mya arenaria were continuously subjected to a flowing raw seawater solution containing a mixture of salts of manganese, zinc, lead, nickel, copper, and cadmium. Final calculated concentrations, in g l^-1, of the toxicant solution were 7200 Mn, 2500 Zn, 70 Pb, 50 Ni, 50 Cu and 1 Cd; these concentrations approximated highest measured levels within surficial interstitial sediment waters from mid-Narragansett Bay, Rhode Island. M. arenaria were also subjected to a 20% solution, i.e., 1440 Mn, 500 Zn, 14 Pb, 10 Ni, 10 Cu, and 0.2 g l^-1 Cd. One study was conducted for 112 days in winter at 0° to 10°C and another for 16 days in summer at 16° to 22°C. In the winter study, all clams exposed to a 100% solution died between the 4th and 10th week; soft parts of survivors at 6 weeks contained about 19 times more Pb, 15 x more Zn, 12 x more Cu, 10 x more Mn, 3 x more Ni and 0.1 x more Cd than controls; relatively minor changes in whole body elemental content of Ca, Cr, Fe, K, Mg, Na, Sr, and V were observed. Clams exposed to a 20% solution during winter survived the 112 day study; at that time these contained about 5 x more Cu, 4 x more Mn, 3 x more Zn and about 2 x more Pb than controls; comparatively minor changes were observed in other elements examined. In the summer study, all M. arenaria subjected to the 100% solution died between 6 and 14 days; survivors from this group at 7 days contained about 25 x more Pb, 13 x more Cu, 11 x more Zn, 7 x more Mn, and 3 x more Ni than controls; other changes in elemental content were not as pronounced. Mortality in the 20% group during summer was slightly higher than controls during the 16 day study; at 14 days survivors from this group contained about 12 x more Mn, 7 x more Pb, 7 x more Zn, 4 x more Cu, and 3 x more Ni than controls. Survival and bioaccumulation patterns were not altered through feeding a supplemental diet of algae. The significance of these findings are discussed in terms of potential environmental perturbations, especially local dredging practices.     

Nutritionally relevant elements in staple foods: influence of arable site versus choice of variety

Eighteen representative sites for the Austrian grain-growing and eight for the potato-growing zones (soils and crops) were investigated. On each site, total element contents (B, Ba, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Sr and Zn) were determined in 4–12 varieties of winter wheat (n = 136), 6 varieties of spring durum wheat (n = 30), 5 varieties of winter durum wheat (n = 15), 7 varieties of rye (n = 49), 5 varieties of spring barley (n = 30) and 5 varieties of potatoes (n = 40). Element accumulations in grain species and potato tubers varied significantly with site conditions, with the main exceptions for B in potatoes and wheat as well as for Zn, Cu and Co in durum wheat. On average, across all investigated sites, differences in varieties occurred concerning the elements Ca, Cd, Ba, Sr and Zn (except Zn in potatoes and winter durum). A rough estimation revealed that an average Austrian consumer of wheat, rye and potatoes meets more than 50% of the needs of daily element intake for K, P and Mg, between 36 and 72% for Fe, Zn and Cu, and more than 100% for Co, Mo and Mn. In particular, the elements Ca and Na have to be added from other sources.     

Toxicity of metals to tadpoles of the common Sunda toad,Duttaphrynus melanostictus

Tadpoles of the common freshwater Sunda toad, Duttaphrynus melanostictus (Amphibia, Bufonidae), were exposed for a 4-day period under laboratory conditions to copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb), nickel (Ni), iron (Fe), aluminum (Al), and manganese (Mn) at various concentrations. Mortality was assessed and median times of death (LT₅₀) and lethal concentrations (LC₅₀) were calculated. LT₅₀ and LC₅₀ increased with the decrease in mean exposure times and concentrations for all metals. LC₅₀ (96?h) for Cu, Cd, Zn, Pb, Ni, Fe, Al, and Mn were 0.03, 0.3, 4.2, 1.5, 8.8, 0.4, 1.9, and 39?mg?L^?1, respectively. Cu was the most toxic to D. melanostictus, followed by Cd, Fe, Al, Pb, Zn, Ni, and Mn (Cu?>?Cd?>?Fe?>?Al?>?Pb?>?Zn?>?Ni?>?Mn). Duttaphrynus melanostictus is similarly sensitive to these metals as other amphibian tadpoles.     

不同地区何首乌无机元素含量的比较

采用ICP法测定了不同地区何首乌植物及其生境土壤中的15种元素(Al、B、Ba、Ca、Cu、Fe、K、Mg、Mn、Na、Ni、P、Sr、Ti、Zn),分析比较了各种元素在不同地区何首乌体内和生境土壤中的分布规律及不同地区何首乌对无机元素的吸收富集能力.结果表明,不同地区何首乌和土壤中无机元素含量存在着显著差异,德庆、井冈山、靖西三地何首乌的Mn含量较高;不同地区何首乌对元素的富集系数无显著性差异,而何首乌对不同无机元素的富集系数则有显著差异,主要表现在对Ca、K、Mg、Sr的吸收富集能力较强.表6参14     

Characteristics,sources and health risk assessment of toxic heavy metals in PM<Subscript>2.5</Subscript> at a megacity of southwest China

Twenty trace elements in fine particulate matters (i.e., PM_2.5) at urban Chengdu, a southwest megacity of China, were determined to study the characteristics, sources and human health risk of particulate toxic heavy metals. This work mainly focused on eight toxic heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The average concentration of PM_2.5 was 165.1 ± 84.7 µg m^?3 during the study period, significantly exceeding the National Ambient Air Quality Standard (35 µg m^?3 in annual average). The particulate heavy metal pollution was very serious in which Cd and As concentrations in PM_2.5 significantly surpassed the WHO standard. The enrichment factor values of heavy metals were typically higher than 10, suggesting that they were mainly influenced by anthropogenic sources. More specifically, the Cr, Mn and Ni were slightly enriched, Cu was highly enriched, while As, Cd, Pb and Zn were severely enriched. The results of correlation analysis showed that Cd may come from metallurgy and mechanical manufacturing emissions, and the other metals were predominately influenced by traffic emissions and coal combustion. The results of health risk assessment indicated that As, Mn and Cd would pose a significant non-carcinogenic health risk to both children and adults, while Cr would cause carcinogenic risk. Other toxic heavy metals were within a safe level.     

Ombrotrophic peat as a medium for historical monitoring of heavy metal pollution

Knowledge of historical trends in heavy metal deposition can aid the study and impact prediction of contemporary pollution. For this purpose, analysis of ombrotrophic peat cores has proved a valuable complement to other sedimentary analyses. However, doubts still remain concerning the mobility of heavy metals in peat. The debate cannot be resolved until the behaviour of these elements in peat is better understood. Peat cores were collected from hollows and hummocks on Ringinglow Bog in the southern Pennines. The cores were sliced into contiguous 1-cm slices. Samples were analysed for total concentrations of major elements (Al, Ca, K, Mg, Na) and trace metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn) using atomic absorption spectrophotometry. Multivariate statistical analysis was conducted on the data. Preliminary results indicate relatively high concentrations of Cd, Cu, Fe, Pb and Zn reflecting the influence of industrial activities in Sheffield and Manchester. As aluminium, cadmium, copper, lead and zinc exhibit similar profiles they may be suitable surrogates for monitoring historical pollution. However, other elements (e.g. Fe, K, Mn, Na) are clearly influenced by bog hydrology or plant translocation and would be inappropriate monitors.     

Source identification of particulate matter and associated intake of elements through inhalation in an industrial area of Odisha,India

Particulate matter concentrations were measured in an industrial region in the Ganjam district of Odisha. The average levels of suspended particulate matter (SPM) were measured to be 142 ± 8 and PM₁₀ of particulate matter with a size of less than 10 micrometers (PM₁₀) to be 50 ± 15 μg m^?3. Out of the 14 elements determined, Ca, Na, Mg, Fe, and K contributed more than 95% of the total weight. In enrichment factors, the trace elements, i.e., Zn, Pb, Cd, and Hg were observed to be highly enriched in the SPM and PM₁₀. Factor analysis indicates that more than 75% of the variance was due to five component factors, which have eigenvalues greater than 1. Intake of elements through inhalation route to adults has been estimated.     

PIXE characterization of PM10 and PM2.5 particulates sizes collected in Ikoyi Lagos,Nigeria

Ambient concentrations of PM₁₀ (x?≤?10?µm) and PM_2.5 (x?≤?2.5?µm) particulate fractions collected from Ikoyi Lagos, Nigeria, as well as their elemental compositions are presented in this study. Both size-segregated fractions were collected using a double staged ‘Gent’ stack filter unit sampler. Elemental characterizations of dust laden filters were carried out using proton-induced X-ray emission (PIXE) technique. Twenty-two elements (Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, Br, Rb, Sr, Zr, Ag, Cd, and Ta) were detected as well as their concentrations and correlations were determined for both particulate size fractions. Their correlation matrix result indicates that some of the trace elements detected could have common source origins or similar chemical properties. The results were similar to the levels observed in moderately polluted urban areas and there is need for source identification and apportionment using receptor models in future studies.     

Neutron activation and atomic absorption analysis of Ulva Lactuca and Gracilaria Verrucosa from Thermaikos Gulf,Greece

NAA and AAS have been applied to determine the content of As, Br, Ca, Cd, Co, Cr, Cu, Fe, K, La, Mn, Na, Ni, Pb, Sb, Sc, Sm and Zn in Ulva lactuca and Gracilaria verrucosa from Thermaikos Gulf, Greece. The analytical data has been subjected to cluster and stepwise discriminant analysis. Thus the influence of some industrial sources on the pollution of water in the Gulf is detected and correlation between Zn‐Co‐Cr‐La; Br‐K; Cu‐Ni; Cd‐Sb‐Mn in the investigated algae is established.     

太湖水华蓝藻中元素的组成及其环境意义

利用电感耦合等离子质谱仪对2008年7、9和10月采自太湖南泉水域的水华蓝藻样本中19种元素(Na、Mg、K、Ca、Zn、Mn、Fe、Al、Cu、Cr、Co、Ni、As、Se、Mo、Ag、Tl、Cd和Pb)的质量含量(w)及组成变化进行研究。结果表明,在藻华中w较高(1 000μg.g-1,以干质量计)的常量元素或有益元素为Ca、K、Na、Mg、Al、Fe。其中,w(Ca)和w(K)较高(4 000μg.g-1),w(Ca)随月份变化不大,而w(K)、w(Mg)、w(Na)则逐月升高。w(Al)、w(Fe)变化较大,7月最高(1 000μg.g-1),之后迅速降低(400μg.g-1);藻华中w在10~100μg.g-1之间变化的元素为Mn、Zn、Ni、Cu,其中,7月这4种元素w均最高,9~10月则降低。藻华中还检出痕量元素Co、Mo和Se,Tl未检出。藻华中积累的有毒元素中w(As)较高(5~15μg.g-1),而w(Cr)、w(Cd)、w(Pb)、w(Ag)均较低(5μg.g-1)。有毒元素w最高值均出现在7月。基于上述结果,推算出2007—2009年采取物理方法除藻从太湖中移除的元素量约为:K595.89 t、Ca 544.03 t、Mg 181.18 t、Al 83.06 t、Na 63.97 t、Fe 55.45 t、Mn 2.99t、Zn 2.26 t、Ni 1.67 t、Cu 1.11 t、As 0.76 t、Cr 94.5 kg、Cd 82.70 kg、Se 45.01 kg、Pb 37.64 kg、Co 32.27 kg、Mo5.41 kg和Ag 2.46 kg。该研究不仅可为进一步寻找关键元素在蓝藻水华爆发过程中的限制作用及其机制提供基础数据,同时也可为评价利用物理除藻方法去除太湖中有毒元素和降低有可能促进藻华发展的营养元素的负荷量的有效性,从而保护和修复渔业环境提供理论依据。     

A contribution to the distribution of some chemical elements inMolinia caerulea andEriophorum vaginatum during reinstatement of the Leegmoor,Emsland, FRG

The concentrations of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Sr, Ti, V and Zn were determined by AES/ICP inMolinia caerulea andEriophorum vaginatum grown in the Leegmoor, which is in reinstatement. In the soil substrate analytical detection limits were obtained for Ag, Co, Li, Mo and Rb and additionally for Al, Be, Cd, Cr, La, Li, Ni, Pb, Ti and V in plants. Compared with mineral soils, the concentration of elements in peat is low. The elements K and P were enriched byMolinia caerulea andEriophorum vaginatum, and in addition Mn and Zn byEriophorum vaginatum. Altogether the ability of accumulation essential elements seem to be more efficient byEriophorum vaginatumthan byMolinia caerulea, which can be an ecophysiological advantage on peats, whereMolinia caerulea is normally not distributed.