The effect of complex formation on the adsorption characteristics of heavy metals

In most aqueous environmental systems, inorganic and organic metal complexes represent a significant contribution to the total soluble metal. Metal adsorption is often a highly pH-dependent phenomena. Such behavior can generally be attributed to changes in metal speciation with solution acidity as well as variation in the extent of surface protonation. Thus, because adsorbability may vary drastically between different metal species, (e.g. Cu²⁺ (aq) compared to CuOH⁺) a knowledge of metal species distribution is essential to understanding and interpreting metal adsorption behavior.Organic complexation has been reported to enhance, suppress and have no perceptible effect on trace metal adsorption. Such differences arise because adsorption depends on factors such as the ligand/metal ratio, adsorbability of the free ligand, and various solution parameters (e.g. pH). Most important in determining the effect of complexation on adsorption is the adsorbability of the resulting complexes. Thus, it is difficult to make generalizations about the influence of organic complexation on metal adsorption.Adsorption of metal complexes is frequently reported to be predominantly coulombic in nature; that is, binding of an anionic or cationic complex to an oppositely charged colloidal particle. However, electrostatic forces can often represent an insignificant contribution to the total free energy of adsorption and can be overshadowed by chemical reactions with the surface, hydrogen bonding, and hydrophobic effects.     

The effects of FeCl3 on the distribution of the heavy metals Cd, Cu, Cr, and Zn in a simulated multimetal incineration system

Recognizing that waste-derived chlorine can enhance heavy metal emissions by forming volatile metallic chlorides during municipal solid waste (MSW) combustion, and that in Taiwan, FeCl3-containing sewage sludge may either be landfilled or coincinerated with other MSW, this study thus investigated the effects of FeCl3 on the speciation and partitioning of heavy metals in a multimetal incineration system by using a tubular furnace and FeCl3-spiked simulated wastes. The molar ratio of chlorine content to heavy metal content (referred to as the Cl/ M ratio), ranging from 3 to 200, was used as a parameter to evaluate the effects of chlorine on the movement of heavy metals between the incinerator discharges. Results indicate that speciation and partitioning were related to the affinity between the chlorine and the heavy metals and between chlorine and hydrogen in the combustion system. The effectiveness of increasing the Cl/M ratio to the formation potential of metallic chlorides and on the shift of heavy metals from the bottom ash to the fly ash and/or the flue gases was found to have in increasing order as follows: Zn>Cu>Cr, a phenomenon basically reflecting the volatility of the heavy metals and their chlorides formed during combustion.     

Characteristics of the PAH emissions from the incineration of livestock wastes with/without APCD

This study was conducted on two batch-type livestock waste incinerators, including the one with an air-pollution control device (APCD)-one wet scrubber (WSB) and the other without APCD for the disposal of livestock wastes. The concentration and composition of 21 individual polycyclic aromatic hydrocarbons (PAHs) in the stack flue gas (gas and particle phases), bottom ash, and effluent of WSB were determined. Stack flue gas samples were collected by a PAH stack-sampling system. Twenty-one individual PAHs were analyzed by a gas chromatography/mass spectrometer (GC/MS). Due to the low combustion temperature, a remarkable and significant increase in the total-PAH concentration of emission from the stack with APCD was observed when compared with the case without APCD. Measured total-PAH emission factors were 285 and 2.86 mg/kg waste for the incineration with and without APCD, respectively, while BaP (the most carcinogenic PAH) emission factors were 0.79 and 0.12 mg/kg waste for the incineration with and without APCD. The total-PAH output/input mass ratios averaged 0.011 and 0.004 with and without APCD, respectively. The result reveals that the PAH content in the auxiliary fuel during the incinerating process could affect the emission of PAH.     

The effect of pollutants (heavy metals and diesel fuel) on the respiratory activity of constructozems (artificial soils)

Young (1 month old) and mature (2 years old) constructozems (artificial soils) were supplemented with individual heavy metal salts or diesel fuel at different concentrations. The polluted and control constructozem variants were incubated and sampled at different time points to determine microbial biomass carbon (C_mic) and microbial respiration (MR). These parameters were found to be almost twice higher in the young than in the mature constructozem, with all pollutants causing an increase in C_mic, MR, and MR/C_mic = qCO₂ values. The pollutant type had an effect on MR and qCO₂ variances, and the time of exposure, on C_mic. The qCO₂ value showed a strong positive correlation with pollutant concentrations, allowing this parameter to be regarded as a suitable indicator of urban environmental pollution.     

PAH emission from the incineration of three plastic wastes

A batch-type, controlled-air incinerator was used for the treatment of polyvinyl chloride (PVC), high-density polyethylene (HDPE), and polypropylene (PP) plastic wastes. The concentration and composition of 21 individual polycyclic aromatic hydrocarbons (PAHs) in the raw wastes, flue gas (gas and particle phases), and ash were determined. Stack flue-gas samples were collected by a PAH stack-sampling system. Twenty-one individual PAHs were analyzed primarily by a gas chromatograph/mass spectrometer (GC/MS). The CO concentration correlated well with the total PAH (R2 > .89), and thus can be used as a surrogate indicator for PAH emission. Excess amounts of air supply in the incineration of plastic wastes could decrease not only the concentration of the PAHs in the bottom ash but also the emission factor (EF) of the total PAH in the stack flue gas. Of the three plastic wastes, HDPE was found to have the highest mean EF of the total PAHs (462.3 mg/kg waste) from the stack flue gas. Incinerating PVC would result in a higher EF of PAHs (195.4 mg/kg waste) in the bottom ash. When PVC plastic wastes were incinerated, higher-ringed PAHs constituted a larger percentage in the bottom ash as compared to those from PP and HDPE plastics. By judging the output and input (O/I) ratio of the PAHs from the incineration trials of plastic wastes, the PAHs involved in incineration of three plastic wastes were almost entirely destroyed; and a low residual amount between 0.00018 and 0.00032 remained in the emission.     

Trends in the dissolution of metals from sediments collected during the Umitaka-Maru cruises using the microwave-acid digestion technique

Sediment samples were collected during the research vessel Umitaka-Maru cruises in the Gulf region from 15–16 December 1993 and 15–27 December 1994, from 19 and 24 locations, respectively. These samples were subjected to trace metal analysis to determine the 1991 Gulf War oil spill environmental impact in the area. The samples investigated are texturally classified into two main sediment classes: sand and mud. The total concentrations of lead, nickel, and vanadium found in the sediments from individual stations were investigated. The differences in trace metal concentrations reflect the variation in the overall composition of their host sediments. To better appraise the trace element composition of their host sediments and to determine the factors governing the trace metal distribution, the data were sub-divided into five groups among 1993 collections and seven groups during 1994. The concentration ranges of all three metals, lead (0.2–4.85), nickel (4.90–86.00), and vanadium (2.00–38.00) varied in different stations among the groups. The partitioning of trace elements between the detrial and non-detrital fractions of the sediments shows that: 1) The high concentrations of elements in mud is coupled with the increase in the detrital fraction; 2) In muddy sand sediments, nickel is bonded to the structural lattice of detrital minerals, whereas vanadium and lead held in the environmentally mobile fraction; and, 3) In sandy mud sediments, Ni is found in the detrital fraction, whereas V to slightly less extent and Pb show their non-detrital nature. The data were compared with unpolluted sediments throughout the ROPME Sea and worldwide, so the effect of anthropogenic enrichment upon the absolute concentration of the elements is minimal.     

The analysis of human health risk with a detailed procedure operating in a GIS environment

An approach for quantifying the human health risk caused by industrial sources, which, daily or accidentally, emit dangerous pollutants able to impact on different environmental media, is introduced. The approach is performed by the HHRA-GIS tool which employs an integrated, multimedia, multi-exposure pathways and multi-receptors risk assessment model able to manage all the steps of the analysis in a georeferenced structure. Upper-bound excess lifetime cancer risk and noncarcinogenic hazards are the risk measures, the spatial distribution of which is calculated and mapped on the involved territory, once all the pathways and receptors of the study area are identified. A sensitivity analysis completes the calculations allowing to understand how risk estimates are dependent on variability in the factors contributing to risk. The last part of the paper makes use of a case study concerning a working industrial site to put in evidence in which way the designed tool can help local authorities and policy makers in managing risks and planning remedial and reduction actions. The considered geographical area is a hypothetical territory characterized by residential, agricultural and industrial zones. The presence of two sources of contamination, a municipal waste incinerator (MWI) and a contaminated site, are evaluated by the tool application. Various typologies of receptors have been taken into account, each of them characterized by different anatomical and dietary properties. The achieved results are analyzed, compared with acceptable and background values and alternatives of minor environmental impact calculated.     

Historical change of heavy metals in urban soils of Nanjing, China during the past 20 centuries

Two typical areas, including once commercial and residential quarters of Nanjing, China, were studied by investigating soil properties especially heavy metals of soils in various cultural layers formed in different Chinese Dynasties. The age of the soil profiles was dated by both archaeological and 14C chronological methods. The results showed that urban soils in the old commercial/workshop quarter of Nanjing were generally contaminated by heavy metals Cu, Zn, Pb, but their concentration levels varied significantly among the cultural layers formed in different dynasties. The substantial increase of heavy metals appeared in three historical periods, i.e., South Dynasty (222-589 AD), the earlier Ming (1368-1644 AD) and the late Qing (1644-1912 AD) in one area. The tremendous input and storage of heavy metals in soils was explained by the primitive smelting and the strengthened metal processing activities, which might be due to the requirement of weapon making or other industries, in the changing social conditions of the corresponding periods. Soils in the once noble political, cultural centers did not show significant increase of heavy metals. The difference in the distribution pattern of heavy metals revealed the contrasting history of the site uses. The change of contaminant level in soils is believed to be a reflection of various human activities in the city during the past 20 centuries.     

Assessment of the environmental contamination with long-lived radionuclides around an operating RBMK reactor station

The presence of man-made gamma emitting radionuclides in the region within 32km radius of the Ignalina NPP/Lithuania has been investigated during the period 2001-2004, prior to the closure of the first of the two operating RBMK 1500-type reactors. Gamma spectrometric measurements of various terrestrial and aquatic plants as well as of soil samples showed moderate environmental contamination with the fission product (137)Cs and with the neutron activation products (60)Co and (54)Mn. Traces of the activation products (65)Zn and (110m)Ag were found in the nearest vicinity of the NPP. Activity concentrations were inhomogeneously distributed in the area of interest. Moss and algae samples showed the highest uptake of radionuclides. In addition to the gamma spectrometric measurements, the levels of (14)C were determined in the same bio-indicator samples using accelerator mass spectrometry.     

The removal of metals and ammonium by natural glauconite

Glauconite deposits, naturally occurring aluminosilicates rich in iron and potassium, are abundant in New Jersey, Delaware, and Maryland. The presence of these deposits has been shown to be responsible for a high content of sodium in ground water for certain region of Maryland. The ammonium and metal (Pb, Zn, and Cd) removal capability was investigated in both batch and column reactors using natural, NaCl- and NaOH-treated glauconite-bearing sand. Ammonium removal by glauconite is a typical ion exchange process. Both ion exchange and adsorption are responsible for matal removal. Important factors such as pH, sample source, and method of pretreatment were studied. The metal removal follows the order of Pb(II) > Zn(II) > Cd(II). The surface acidity of the glauconite is characterized by an acidmetric-alkalimetric titration. The acidity constants, pK₁ⁱ, and pK₂ⁱ, and 3.6 and 6.0, respectively.     

The effect of environmental conditions of the open channel period on the relative body condition of semianadromous burbot,Lota lota L. (Lotidae), in the Ob River

The results of long-term observations on changes in the relative body conditions of burbot (Lota lota L.) in the Lower Ob basin during the open channel period (June–September) are analyzed. Statistically significant strong positive dependence of the hepatosomatic index of spawners on the maximum flood level is revealed. An equation predicting the value of the hepatosomatic index of spawners from instrumentally measurable environmental parameters is constructed.     

The holocene dynamics of vegetation and environmental conditions on the eastern slope of the Northern Urals

Consideration is given to changes in the vegetation and climatic conditions on the eastern slope of the Northern Urals in the second half of the Holocene as reconstructed on the basis of integrated palynological, botanical, paleocarpological, and radiocarbon analysis of material from a peat bog section in the floodplain of the Loz’va River. The results show that the northern taiga zone of the study region in the period between approximately 5000 and 700 years BP was occupied by forests of southern taiga facies, as the climate was significantly warmer than it is today.     

The Holocene dynamics of vegetation and climatic conditions on the eastern slope of the Subpolar Urals

Changes in the vegetation and climatic conditions on the eastern slope of the Subpolar Urals over the past 10000 years have been reconstructed on the basis of integrated palynological, botanical, and radiocarbon analysis of material from two sections of peat deposits in the floodplains of the Lyapin and Man’ya rivers (the Severnaya Sos’va basin). The dynamics of regional vegetation have been traced: from the herb–shrub tundra in the late postglacial time to the spruce–larch forest–tundra and sparse larch–birch–spruce stands in the Early Holocene, to birch–pine–spruce forests with an admixture of fir in the Middle Holocene, and to northern taiga forests with dominance of Scots pine and Siberian stone pine (similar to present-day forests) in the Late Holocene. The results show that the northern taiga zone of the study region in the period between approximately 5500 and 2500 years BP was occupied by forests of middle and southern taiga facies, as the climate was significantly warmer than it is today.     

Introduction to and experimental conditions during the first year of the GMR chronic inhalation studies of diesel exhaust

A chronic exposure study was initiated to determine the effects of diesel exhaust on the health of experimental animals. For this purpose, test atmospheres of clean air (control) or freshly diluted diesel exhaust at concentrations of 250, 750, and 1500 μg/m³ were supplied to four 12.6 m³ inhalation chambers which housed rats and guinea pigs. Diesel aerosol size and concentration, as well as chamber temperature and relative humidity, were continually monitored and controlled to maintain the exposure dose levels and an environment of 22±2°C and 50%±20% relative humidity. The concentrations of CO and NO_x were found to be 5.8±1.0 mg/m³ and 7.9±1.0 mg/m³ above ambient in the chamber containing 1500 μg/m³ of particulate. Animals were supplied from the chambers, on a random basis, for both intramural and extramural studies throughout the exposure period. The experiment ran uninterrupted for over twelve months with mean diesel particle mass concentrations within 2% of the target values.     

Heavy metals in agricultural soils of the European Union with implications for food safety

Soil plays a central role in food safety as it determines the possible composition of food and feed at the root of the food chain. However, the quality of soil resources as defined by their potential impact on human health by propagation of harmful elements through the food chain has been poorly studied in Europe due to the lack of data of adequate detail and reliability. The European Union's first harmonized topsoil sampling and coherent analytical procedure produced trace element measurements from approximately 22,000 locations. This unique collection of information enables a reliable overview of the concentration of heavy metals, also referred to as metal(loid)s including As, Cd, Cr, Cu, Hg, Pb, Zn, Sb. Co, and Ni. In this article we propose that in some cases (e.g. Hg and Cd) the high concentrations of soil heavy metal attributed to human activity can be detected at a regional level. While the immense majority of European agricultural land can be considered adequately safe for food production, an estimated 6.24% or 137,000 km² needs local assessment and eventual remediation action.     

The influence of uncertainty and location-specific conditions on the environmental prioritisation of human pharmaceuticals in Europe

The selection of priority APIs (Active Pharmaceutical Ingredients) can benefit from a spatially explicit approach, since an API might exceed the threshold of environmental concern in one location, while staying below that same threshold in another. However, such a spatially explicit approach is relatively data intensive and subject to parameter uncertainty due to limited data. This raises the question to what extent a spatially explicit approach for the environmental prioritisation of APIs remains worthwhile when accounting for uncertainty in parameter settings. We show here that the inclusion of spatially explicit information enables a more efficient environmental prioritisation of APIs in Europe, compared with a non-spatial EU-wide approach, also under uncertain conditions. In a case study with nine antibiotics, uncertainty distributions of the PAF (Potentially Affected Fraction) of aquatic species were calculated in 100 1 100 km² environmental grid cells throughout Europe, and used for the selection of priority APIs. Two APIs have median PAF values that exceed a threshold PAF of 1% in at least one environmental grid cell in Europe, i.e., oxytetracycline and erythromycin. At a tenfold lower threshold PAF (i.e., 0.1%), two additional APIs would be selected, i.e., cefuroxime and ciprofloxacin. However, in 94% of the environmental grid cells in Europe, no APIs exceed either of the thresholds. This illustrates the advantage of following a location-specific approach in the prioritisation of APIs. This added value remains when accounting for uncertainty in parameter settings, i.e., if the 95th percentile of the PAF instead of its median value is compared with the threshold. In 96% of the environmental grid cells, the location-specific approach still enables a reduction of the selection of priority APIs of at least 50%, compared with a EU-wide prioritisation.     

Effect of boric acid on the ability of plants to accumulate heavy metals

The effect of boric acid on the ability of herbaceous plants to absorb heavy metals has been studied. The results show that at a low content of boron in sandy loam soil (0.0007 mg/kg dry matter), boric acid at doses of 0.1–3.0 kg/ha stimulates the accumulation of certain heavy metals in the aboveground part of plants from the families Asteraceae (Taraxacum officinale Wigg.), Poaceae (Phleum pratense L.), and Fabaceae (Trifolium pratense L.). The most active accumulation is characteristic of dandelion (T. officinale) plants, which allows this species to be considered promising for phytoremediation of soils with a low boron content given that boron is applied at specified doses.     

The effect of iron on the biological activities of erionite and mordenite

Epidemiological data has demonstrated that environmental and/or occupational exposure to mineral particulates may result in the development of pulmonary fibrosis, bronchogenic carcinoma and malignant mesothelioma many years following exposure. It has been suggested that the genotoxic effects of fibrous particulates, such as asbestos, is due in part to the generation of reactive oxygen species (ROS) from iron associated with the particulates. However, the molecular mechanisms by which mineral particulates induce ROS that results in genotoxic damage remains unclear. The naturally occurring zeolites, erionite and mordenite share several physiochemical properties but they elicit very different biological responses, with erionite, a fibrous particulate, being highly toxic, and mordenite, a nonfibrous particulate, being relatively benign. We are using these natural zeolites as a model system to determine what physicochemical properties of these zeolites are responsible for their biological response(s) and to evaluate the parameters that influence these responses. The purpose of the present study was to determine the mutagenic potential of erionite and mordenite and to determine whether this mutagenic potential was modulated by iron. The results of this study using the Chinese hamster ovary cell line AS52 demonstrated that erionite was more cytotoxic than mordenite. However, the cytotoxicity of both zeolites was increased in the presence of physiological concentrations of ferrous chloride. Ferrous ions (5-20 microM) significantly (p<0.001) increased the cytotoxicity of mordenite, but only at the highest concentration (16 microg/cm(2)) of mordenite tested. Conversely, only the highest concentration (20 microM) of ferrous ion significantly (p<0.001) increased the cytotoxicity of erionite, but this enhanced cytotoxicity occurred over a wider concentration range (6-16 microg/cm(2)) of erionite. Mordenite was not mutagenic at any of the concentrations tested, and the mutagenic potential of mordenite was not enhanced by the addition of ferrous ion. Conversely, erionite was mutagenic in a dose-response manner at concentrations greater than 6 microg/cm(2) and the mutagenic potential of erionite was significantly enhanced by the addition of ferrous ions. These results suggest that while the cytotoxicity of mordenite and erionite may be related to the ability of these fibers to transport iron into a cell, the different coordination state of iron associated with the two fiber surfaces is critical for inducing genotoxic damage.     

Impact of trace metals and nutrients levels on phytoplankton from the Kuwait coast

The impact of marine pollution was estimated from seven stations of Kuwait coastal waters. The mean concentrations of all trace metals in seawater (0.07-7.04 microg/l) and in phytoplankton (14.90-52.01 microg/g) revealed less phytoplankton abundance in Stations IV VI during the four seasons. However, a relative surge in the phytoplankton abundance, with an increase in the mean concentrations of all trace metals in seawater (0.15-8.94 microg/l) and phytoplankton (22.82-61.25 microg/g), was observed in Station II. A low phytoplankton abundance was noted in Stations I, III, and VII despite low mean concentrations of all the trace metals in seawater (0.11-5.77 microg/l) and phytoplankton (1.40-20 microg/g) during the four seasons. Statistical tests revealed significant difference in Fe, Ni, and Pb between the four seasons in seawater and Fe and Co in phytoplankton. No significant difference in trace metals between locations was observed in seawater and in phytoplankton. The major nutrients in all the four seasons were found in the magnitude of SiO3 > NO3 > PO4 in all the stations, and thus, support the presence of rich diatoms and dinoflagellates than other phytoplankton groups. The seven stations also represented indicator species of oil and industrial waste pollution.