Calcareous electrochemical precipitation,a new method to trap nickel in seawater

There are few efficient, rapid and cheap methods to remove toxic metals from contaminated waters. Here we hypothesised that cathodic protection, an existing method used to control the corrosion of metallic structures, may trap toxic metals. Indeed, in seawater, the application of a cathodic current on a metallic structure induces the precipitation of limestone (CaCO₃) and magnesium dihydroxyde (Mg(OH)₂), thus forming a calcareous deposit on the metal surface. We therefore presumed that such calcareous deposit may trap metals dissolved in waters. Actually calcareous deposit formation has never been studied in the presence of dissolved metallic contaminants such as nickel. Here we tested ionic nickel (Ni²⁺) precipitation in calcareous deposit with a galvanized steel electrode by spiking artificial seawater with a NiCl₂ salt during 7 days of applied current. We analysed deposit surface and cross section by µ-Raman spectroscopy and scanning electron microscopy (SEM) with X-ray microanalysis. Ni concentration in the deposit was quantified by inductively coupled plasma analysis, after deposit dissolution in 60% HNO₃. Results show that in 7 days up to 24% of nickel can be trapped in the calcareous deposit. Scanning electron microscopy reveals that Ni is trapped under a pure CaCO₃ layer of aragonite. Raman spectra show that nickel is incorporated as nickel dihydroxyde (Ni(OH)₂), as evidence by vibration bands at 446 and 510 cm^?1. Overall our findings disclose a new and efficient method, calcareous electrochemical precipitation, which has potential applications to remove toxic metals from contaminated waters.     

Large-scale disinfection of real swimming pool water by electro-oxidation

Swimming pool users are a source of various contaminants and microorganisms. Conventional chlorine-based reagents treatment is commonly used to disinfect water. However, this disinfection treatment has serious serious health issues such as formation of carcinogenic by-products, i.e., trihalomethanes. In order to prevent this problem, an electrochemical disinfection process was carried out using synthetic and real swimming pool waters. The performance of the electrochemical system was evaluated by studying the effect of current intensity (0.5–3.0 A), treatment time, type of anode (Nb/BDD and Ti/Pt) and the initial concentration of pathogens Escherichia coli and P. aeruginosa. Results show that real swimming pool water, initially containing 10⁶ CFU/100 mL of pathogens, was disinfected at current intensities of 1.5 and 3.0 A using, respectively, Nb/BDD and Ti/Pt as anode materials (CFU: colony-forming units, BDD: boron-doped diamond). This work is also one of the few showing the up-scaling of electrochemical disinfection of real swimming pool water at large volumes of 100 L.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO₃) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0–5% powdered eggshell waste and curing the soil (1,246 mg Pb kg^?1 soil and 17 mg Cd kg^?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl₂), 1 M CaCl₂, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH₃COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO₃ and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO₃ and eggshell waste, regardless of extractant. Using CaCl₂ extraction, the lowest Cd concentration was achieved upon both CaCO₃ and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH₃COOH or EDTA in soils treated with CaCO₃ and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO₃ for the immobilization of heavy metals in soils.     

Precipitation of aragonite by calcitic bivalves in Mg-enriched marine waters

To understand the relative importance of biological versus physicochemical control over biomineralization, we have tested if the chemical composition of the medium (i.e., the Mg/Ca ratio) can change the mineralogy of mollusk shells. The shells of mollusks are made of calcite and/or aragonite, which are by far the most common CaCO₃ polymorphs. Several species of bivalves with predominantly calcitic shells have been cultivated in artificial seawater with a Mg/Ca molar ratio within the range of 8.3–9.2, well above the present value for seawater (5.2). Four out of six species used (the scallop Chlamys varia, the oyster Ostrea edulis, the saddle oyster Anomia ephippium and the mussel Mytilus edulis) survived long enough to secrete significant amounts of calcium carbonate. The deposits (sometimes extensive) formed on the interior shell surfaces were predominantly aragonitic. Three individuals of C. varia also increased their length by adding new shell at the margin. Contrary to the internal shell deposits, these margins were high-Mg calcite. This implies that the marginal mantle is able to exert a more strict control on the secreted mineral phase than the mantle facing the internal shell surface. This is the first report on an in vivo experimentally forced switch in bivalve shell mineralogy, from calcite to aragonite due to a change in water chemistry.     

(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey

Background

Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and –furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible.

Results

Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40–268 ng g^?1) followed by emerging flame retardants (0.5–7.7 ng g^?1), polybrominated diphenyl ethers (PBDE; 0.3–3.7 ng g^?1), hexabromocyclododecane (HBCD; 0.3–1.2 ng g^?1), dl-PCB (0.04–0.4 ng g^?1) and PCDD/F (0.008–0.06 ng g^?1).

Conclusions

Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol–air partition coefficient (K_OA) and octanol–water partition coefficient (K_OW).

     

Chemical and structural characteristics of statoliths from the short-finned squid Illex illecebrosus

Statoliths of the short-finned squid Illex illecebrosus were chemically analyzed to define their chemical composition and surveyed by scanning electron microscope to differentiate internal structural patterns. X-ray diffraction data demonstrated that I. Illecebrosus statoliths were composed principally of CaCO₃ in the aragonite crystal form. The crystals occurred in a protein matrix to form incremental patterns which radiated from the nucleus to the edge of the statoliths. The protein matrix comprised approximately 5% of the statolith by weight. The protein was principally composed of acidic amino acids. A high abundance of aspartic acid in the protein matrix indicated that the matrix would function as a template in the initiation and acceleration of the crystal growth of CaCO₃. The rhythmic microstructural patterns, constructed of aragonite crystals in the protein matrix, were suggested to be daily in formation and subsequent growth estimations were in agreement with known life history information. The stable isotopic composition of the carbonate of I. illecebrosus statoliths suggested that oxygen may be deposited in isotopic equilibrium with the surrounding environment while carbon appeared to be related to biological processes. The information recorded in the statoliths as incremental growth and stable isotopic composition could provide valuable insights into the ecological history of squid.     

Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

Sources,spatial variation,and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Subsurface geochemical behavior of As(V) with Fe(II) was studied under strict anoxic conditions. Abiotic reduction of As(V) (0.1 mM) to As(III) by aqueous Fe(II) and sorbed Fe(II) in pH range 5.0–7.0 and Fe(II)_aq concentration (0.6–1.2 mM) was investigated along with the effect of As(V) on the oxidation of Fe(II) by dissolved oxygen (DO). Although the reduction was thermodynamically feasible for homogeneous chemical conditions, practically no As(V) reduction by aqueous Fe(II) was observed. Similarly, no sorbed As(V) reduction was observed under the heterogeneous experimental conditions by sorbed Fe(II) onto synthetic iron oxide (hematite, α-Fe₂O₃). Experimental results on Fe(II) oxidation by DO in the presence of 0.1 mM As(V) showed a significantly slower Fe(II) oxidation, which might be due to the formation of Fe(II)–As(V) complex in the aqueous phase. The results of this study demonstrate that As(V) is relatively stable in the presence of Fe(II) under subsurface environment and interfere the oxidation of Fe(II).     

A morphological and structural study of the larval shell from the abalone <Emphasis Type="Italic">Haliotis tuberculata</Emphasis>

The larval shell of the marine gastropod Haliotis tuberculata was investigated by polarised light microscopy, scanning electron microscopy, Raman microspectroscopy and infra-red spectroscopy. Trochophore and veliger larval sections were used for histological examination of the growing shell and each larval stage was related to the shell development and the appearance of calcified formations. We determined the stage of initial calcification by specific staining combined with polarised light examination. The shell of 30-h-old pre-veliger larvae was found to be mineralized, confirming that calcification occurred before larval torsion. Using both infra-red and Raman spectroscopy, we showed that CaCO₃ deposition occurred at the pre-veliger stage and that the mineral phase initially deposited was essentially composed of aragonite.     

Carbon- and oxygen-isotope composition of the cuttlebone of Sepia officinalis: a tool for predicting ecological information?

Analysis of the isotope composition of calcareous structures of marine organisms has proved useful in providing biological data. The present study constitutes the first detailed work undertaken on the isotope composition of coleoid cephalopods. We analysed the carbon- and oxygen-isotope composition [δ¹³C (CO²⁻ ₃) and δ¹⁸O (CO²⁻ ₃), respectively] of the cuttlebone aragonite of wild and cultivated specimens of Sepia officinalis Linnaeus, 1758. δ¹³C (CO²⁻ ₃) ranged from −2.94 to 1.00‰, δ¹⁸O (CO²⁻ ₃) from −0.18 to 2.08‰. The carbon-isotope composition is not in equilibrium with the carbon species of the ambient seawater, and does not reflect the deposition of CaCO₃ in seawater. The potential influence of environmental factors and biological processes on the carbon-isotope composition of the cuttlebone is discussed. In contrast to δ¹³C, the oxygen-isotope composition of cuttlebone aragonite appears to be in isotopic equilibrium with the ambient seawater. Seasonal changes in isotopic temperature revealed by our analyses agreed with changes in the temperature of the ambient seawater. CaCO₃ was deposited all year round. A maximum life span of 2 yr, a year-round spawning season, and variable growth rates among and within individuals have been inferred from the isotopic temperatures. Received: 14 April 1998 / Accepted: 26 November 1998     

Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis

Study of uranium interstitial compositions of non-stoichiometric oxides UO_2+x (x ∈ 0.1–0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25–300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO_2.66·yUO_2.33, xUO_2.66·yUO_2.33/SiO₂, xUO_2.66·yUO_2.33/SiO₂ (NaOH) and SiO₂/x′NaOH·y′UO₂(NO₃)₂·6H₂O, multicomponent systems (x = 1, y ∈ 0.1–1.0 and x′ = 1, y′ ∈ 0.1–0.6) as well as phase transitions UO₂(NO₃)₂·6H₂O → {U₄O₉(UO_2.25)} → U₃O₇(UO_2.33) → U₃O₈(UO_2.66) → {UO₃}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO _2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO₂ is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO_1.65–UO_2.25 has occurred due to radiolysis of water on UO₂ surface yielding to H₂O₂, OH^·, and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol–attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.     

X-ray diffraction study of the first larval shell of Ostrea edulis

X-ray powder diffraction was used to study the calcification of the first larval shell of Ostrea edulis (sampled in Limski kanal, Istria, Adriatic Sea in April 1986) from the trochophore stage to the veliger larvae (prodissoconch I), and development of the latter up to several days postfertilization (prodissoconch II). In the first stage, only the amorphous component is present (periostracum and organic matrix). The beginning of shell formation is manifested by the appearance of calcite (up to 1–4% of the total vol.) and then aragonite (2 to 7%). In a later stage of the veliger larvae the fraction of calcite decreases, as well as the fraction of the amorphous component, while the fraction of aragonite rapidly increases. In the prodissoconch II stage, aragonite is dominant, with a very small amount of amorphous component and traces of calcite. In contrast, the valves of the adult O. edulis are composed mainly of calcite, with traces of aragonite.     

X-ray diffraction study of mineral components in calcareous algae (Corallinaceae,Rhodophyta)

The mineral composition of nine species of red calcareous algae (Corallinaceae, Rhodophyta) collected in the Adriatic Sea in 1987 and 1988 was examined by X-ray powder diffraction (counter diffractometer, monochromatized CuK radiation). In addition, a comparison between the calcareous algae from the north Adriatic (Rovinj area) and the central Adriatic (Kornati Islands) with regard to genus, species and environmental factors was undertaken. All analyzed samples contained magnesium calcite, which was dominant in all but in two cases, where aragonite was the main phase. Diffraction lines of magnesium calcite were broadened and shifted toward higher Bragg angles in relation to pure calcite. Supposing that in the calcite crystal lattice only magnesium replaces calcium, it follows that the fraction of magnesium in magnesium calcite, found from diffraction line shifts, would be 18 molar % (M%). Aragonite was dominant (75 to 80 M%) in two samples of Pseudolithophyllum expansum collected at Kornati Islands in 1987 and 1988. These two samples also contained magnesium calcite and a small fraction of calcite (5 to 10 M%). In other studied samples aragonite was detected in small fractions, up to 10 M%. The elemental analysis of corallinacean algae obtained by X-ray spectroscopy showed that the fraction of the metals Sr, Fe, Mn, Zn, Pb, Br, Cu and Rb was very small (15 to 2000 ppm). In most samples other expected minerals were detected in small fractions, such as sylvite (KCl, up to 2 M%), quartz (-SiO₂, up to 2 M%) and magnesite (MgCO₃, only in one sample, 1 M%). The results show that calcareous algae are able to deposit a mixture of magnesium calcite, calcite and aragonite. Such a large molar fraction of aragonite in the alga P. expansum, or in any other corallinacean algae, has not been noted in recent literature. It seems that a complexity of microclimatic and oceanographic factors may influence the diversity of two localities and cause some exchange in living organisms. In addition, the fact that under certain conditions the same organism is capable of forming different minerals from the same tissue (McConnaughey 1989) confirms our opinion that environmental effects are imprinted in the skeletal composition of calcareous algae P. expansum.     

Acid dissolution methods for heavy metals determination in pine needles

Microwave digestion procedures using HNO₃, HNO₃+H₂O₂, HNO₃+HClO₄, HF mixtures and dry ashing with HF were investigated for heavy metals analysis by either inductively coupled plasma-optical emission spectroscopy (ICP-OES) or ICP-mass spectrometry (ICP-MS) in pine needles. The HF digestion procedures gave about 1.5 times higher values than a mixture of HNO₃+H₂O₂ alone. For Ti determination in needles, the HF procedure using dry ashing is thus recommended. The mean concentrations amounted to 900 mg/kg for Fe and 21.8 mg/kg for Ti in needles collected at an area polluted by a stainless steel works. Those concentrations were 10.6 and 4.3 times higher than in needles collected at an area nearby a pulp mill complex (84.5 mg/kg Fe and 5.0 mg/kg Ti).     

TiO<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript> nanoparticles – Relationship between dispersion preparation method and ecotoxicity in the algal growth test

PurposeLittle is known about the ecotoxicity of nanomaterials and there are no specific guidelines for sample preparation and testing. We set out to establish whether the method used to prepare TiO₂ dispersions had a significant impact on aquatic ecotoxicity. We also followed the formation of agglomerates during the incubation period.MethodsWe applied the algal growth inhibition test (OECD test guideline no. 201). Dispersions were prepared by stirring and/or ultrasonication for different durations, and by filtration according to an OECD procedure recommended for testing difficult substances.ResultsSamples stirred for 7?d were not toxic, but EC₂₀ values could be calculated for all the other treatments. Shorter treatments generated EC₂₀ values in the range 1–27?mg/L. Only the shortest treatment (1 min stirring, 1 min ultrasonication) produced an unusually high EC₂₀ value, indicating low toxicity. Development of agglomerate size and of toxicity depends on the nanoparticles. We found that ecotoxicity was predominantly caused by a fraction of nanoparticles and agglomerates obtained by passing dispersions through a 0.22-µm filter.ConclusionsWe propose a short treatment regime to generate the most relevant ecotoxicity data for TiO₂, for example stirring for 1?min followed by 3 min ultrasonication. Until more data concerning the ecotoxicity of different fractions are available, we recommend the testing of unfiltered dispersions rather than filtrates. Relating ecotoxicity to the total hydrodynamic surface of the nanomaterials rather than concentration does not seem to improve the accuracy of ecotoxicity assessments using the algal growth inhibition test.     

Titanium dioxide nanoparticles induce bacterial membrane rupture by reactive oxygen species generation

Nano-titania is widely used in the food industry due to its efficient antimicrobial activity. However, the mechanism of microbial toxicity of nano-titania is poorly known. Here, nano-TiO₂ has been fabricated by microwave-irradiation chemistry, a new method, and then tested for antimicrobial activity. Mutagenicity of nano-TiO₂ was evaluated using Salmonella typhimurium histidine-auxotrophic strains. The reactive oxygen generation test was performed using 2,7-dichlorofluorescein diacetate dye. To test membrane permeabilization, E. coli cultures were grown in nutrient broth at an optical density of 0.3–0.5 at 610 nm, harvested by centrifugation at 11,000g for 10 min, washed and resuspended in 0.5 % NaCl solution. We also analyzed superoxide formation and membrane integrity, and we used scanning electron microscopy. Results show that nano-TiO₂ has a minimum inhibitory concentration of 15 µg/mL, and a minimum bactericidal concentration of 20 µg/mL for E. coli. The bacterial inner wall was ruptured, and cytoplasmic content was released after 5 min of treatment in a dose-dependent manner. Notably, superoxide formation was not observed, which establishes the fact that reactive oxygen generation and alteration of membrane integrity, as well as permeability, is the major mechanism of antimicrobial activity of nano-TiO₂.     

Impact of logging activities in a tropical mangrove on ecosystem diversity and sediment heavy metal concentrations

Productivity of mangrove ecosystems is compromised by anthropogenic activities including over-exploitation of wood. This study set out to understand how different wood harvesting regimes have affected the biodiversity of a tropical ecosystem and to identify relationships between the heavy metal concentrations in the mangrove sediments and tree felling. Soil samples were collected and plant diversity studies carried out on seven sites in the mangrove. Physico-chemical, chemical and mineralogical analyses were done on soil samples and plant population structure, species richness, evenness and diversity index at these sites were calculated. Results showed that soils across sites were characteristically clayey and acidic, with high organic matter content. Minerals identified included quartz, gibbsite, goethite, hematite and kaolinite. Heavy metal concentrations were higher in Sites 6 and 7 with a longer history of anthropogenic activity. There were strong negative correlations between the duration of logging and NO₃-N (r = ?0.838, p = 0.019), total N (r = ?0.837, p = 0.019), NH₄ ⁺-N (r = ?0.844, p = 0.017), Mg = (?0.789, p = 0.035), K (r = ?0.819, p = 0.024), and Na (r = ?0.988, p = 0.002). Sites which had experienced logging for longer periods (sites 3, 6, and 7) had lower nutrient content and lower values for species richness and diversity index. Logging in mangrove ecosystems could alter soil characteristics, decreasing plant diversity and abundance. Logging dynamics around mangrove ecosystems should be considered in the wider strategy for management and conservation of similar mangrove ecosystems.     

Effect of chemical amendments on remediation of potentially toxic trace elements (PTEs) and soil quality improvement in paddy fields

Remediation of potentially toxic trace elements (PTEs) in paddy fields is fundamental for crop safety. In situ application of chemical amendments has been widely adapted because of its cost-effectiveness and environmental safety. The main purpose of this research was to (1) evaluate the reduction in dissolved concentrations of cadmium (Cd) and arsenic (As) with the application of chemical amendments and (2) monitor microbial activity in the soil to determine the remediation efficiency. Three different chemical amendments, lime stone, steel slag, and acid mine drainage sludge, were applied to paddy fields, and rice (Oryza sativa L. Milyang 23) was cultivated. The application of chemical amendments immobilized both Cd and As in soil. Between the two PTEs, As reduction was significant (p < 0.05) with the addition of chemical amendments, whereas no significant reduction was observed for Cd than that for the control. Among six soil-related variables, PTE concentration showed a negative correlation with soil pH (r = ?0.70 for As and r = ?0.54 for Cd) and soil respiration (SR) (r = ?0.88 for As and r = ?0.45 for Cd). This result indicated that immobilization of PTEs in soil is dependent on soil pH and reduces PTE toxicity. Overall, the application of chemical amendments could be utilized for decreasing PTE (As and Cd) bioavailability and increasing microbial activity in the soil.     

Blood concentrations of lead,cadmium, mercury and their association with biomarkers of DNA oxidative damage in preschool children living in an e-waste recycling area

Reactive oxygen species (ROS)-induced DNA damage occurs in heavy metal exposure, but the simultaneous effect on DNA repair is unknown. We investigated the influence of co-exposure of lead (Pb), cadmium (Cd), and mercury (Hg) on 8-hydroxydeoxyguanosine (8-OHdG) and human repair enzyme 8-oxoguanine DNA glycosylase (hOGG1) mRNA levels in exposed children to evaluate the imbalance of DNA damage and repair. Children within the age range of 3–6 years from a primitive electronic waste (e-waste) recycling town were chosen as participants to represent a heavy metal-exposed population. 8-OHdG in the children’s urine was assessed for heavy metal-induced oxidative effects, and the hOGG1 mRNA level in their blood represented the DNA repair ability of the children. Among the children surveyed, 88.14% (104/118) had a blood Pb level >5 μg/dL, 22.03% (26/118) had a blood Cd level >1 μg/dL, and 62.11% (59/95) had a blood Hg level >10 μg/dL. Having an e-waste workshop near the house was a risk factor contributing to high blood Pb (r _s  = 0.273, p < 0.01), while Cd and Hg exposure could have come from other contaminant sources. Preschool children of fathers who had a college or university education had significantly lower 8-OHdG levels (median 242.76 ng/g creatinine, range 154.62–407.79 ng/g creatinine) than did children of fathers who had less education (p = 0.035). However, we did not observe a significant difference in the mRNA expression levels of hOGG1 between the different variables. Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels (β _Q2 = 0.362, 95% CI 0.111–0.542; β _Q3 = 0.347, 95% CI 0.103–0.531; β _Q4 = 0.314, 95% CI 0.087–0.557). Associations between blood Hg levels and 8-OHdG were less apparent. Compared with low levels of blood Hg (quartile 1), elevated blood Hg levels (quartile 2) were associated with higher 8-OHdG levels (β _Q2 = 0.236, 95% CI 0.039–0.406). Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels.     

Validation of a digestion procedure for ICP-AES and dynamic reaction cell ICP-MS for trace elemental analysis in environmental samples

Due to chloride polyatomic interferences, hydrochloric acid is not recommended for preparation of samples analysed by ICP-MS and separate digestion procedures are used for ICP-MS and ICP-AES. Here we demonstrate that a single digestion procedure using a mixture of HNO₃ and HCl can be used for ICP-AES and dynamic reaction cell (DRC)-ICP-MS. Hotplate, block digester and microwave digestion were investigated. For a quantitative recovery of 26 elements including Ag, Sb and Ti from waters, soils and sediments, the final concentration of 10% (v/v) HCl in the digest is required regardless of the digestion techniques. The method detection limits of 0.3–1.2 μg/L were obtained for chloride-interfering elements As, V, Cr and Se by DRC-ICP-MS using ammonia and oxygen as the DRC gas.