Analysis of heavy metals in ecstasy tablets by electrochemical methods

Trace amounts of heavy metals have been analysed by electrochemical techniques in ecstasy tablets obtained from different police seizures in Spain. Lead, cadmium, copper and zinc were determined by differential-pulse anodic stripping voltammetry at a hanging mercury drop electrode, whereas nickel and cobalt were determined by adsorptive differential-pulse cathodic stripping voltammetry from their dimethylglyoxime complexes, M(DMG)₂. The performance of the procedure was compared with electrothermal atomic absorption spectrometry. The procedure was applied to the determination of these elements in nine ecstasy samples, finding that Zn is the element present in the highest concentration, ranging from 0.3 to 200?mg?kg^?1, Ni, Cu appear below 15?mg?kg^?1 and Pb below 8?mg?kg^?1, while Cd and Co levels were always lower than 0.51?mg?kg^?1.     

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).     

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.     

Effects of specimen handling and otolith preparation on concentration of elements in fish otoliths

The use of otolith chemistry as a tool for analysing the biology of fishes assumes that the procedures used to collect and prepare otoliths for analysis do not alter their composition. With otoliths of Nemadactylus macropterus, Hoplostethus atlanticus, and Rhombosolea tapirina, we show that this assumption is not valid for the elements that can be detected using electron-probe microanalysers (those present at concentrations greater than ≃100 parts per million): all six elements routinely measured using these techniques were affected by at least one post-mortem procedure tested. Measured concentrations of calcium and strontium were relatively insensitive to most procedures tested, whereas concentrations of sodium, potassium, sulphur and chlorine were affected substantially by many commonly used procedures. The ease with which otolith composition could be modified post-mortem suggests that apparent geographic, habitat-specific or ontogenetic differences in otolith composition should be interpreted with extreme caution because of easily induced artefacts and the problem of pseudo-replication associated with the ways otoliths are sampled and prepared for analysis. Received: 23 September 1996 / Accepted: 11 April 1998     

Cluster analysis of inorganic elements in particulate matter in the air environment of an equatorial urban coastal location

Concentrations of nine inorganic elements (Na, Zn, Ca, Fe, Ni, Mn, Cu, Cd and Al) in particulate matter (PM₁₀) in the air of an equatorial urban coastal location during 2009 were studied during summer and winter monsoon seasons using high-volume sampling techniques. Atomic absorption spectrophotometry was used to analyse the samples. The concentrations of most inorganic elements were higher during summer than winter, except for Cu and Zn. The main inorganic elements in PM₁₀ are Na, Zn and Ca. High concentrations of Na and Ca are due to marine aerosols. Analysis of enrichment factors showed that inorganic elements are from non-crustal sources. Cluster analysis identified five clusters in the summer and six in the winter: (1) PM₁₀–Ni, (2) Zn–Na, (3) Fe–Cu–Ca–Cd, (4) Mn and (5) Al for summer; and (1) PM₁₀, (2) Zn, (3) Fe–Ni, (4) Cu–Ca–Na–Cd, (5) Mn and (6) Al for winter. Combining both correlation and cluster analysis, it was found that Fe–Cu–Cd was from industry/vehicle emissions, Zn was from resuspended soil, Mn was from metallurgical processes, Ni was from a nearby power plant and Al was from crustal sources. Inorganic element concentrations could be a good indicator of local sources of PM₁₀.     

The pollution characteristics of PM<Subscript>2.5</Subscript> and correlation analysis with meteorological parameters in Xinxiang during the Shanghai Cooperation Organization Prime Ministers’ Meeting

The pollution characteristics of PM_2.5 and correlation analysis with meteorological parameters in Xinxiang during the Shanghai Cooperation Organization Prime Ministers’ Meeting were investigated. During the whole meeting, nine PM_2.5 samples were collected at a suburban site of Xinxiang, and the average concentration of PM_2.5 was 122.28 μg m^?3. NO₃ ^?, NH₄ ⁺, SO₄ ^2? accounted for 56.8% of the total water-soluble ions. In addition, with an exception of Cl^?, all of water-soluble ions decreased during the meeting. Total concentrations of crustal elements ranged from 6.53 to 185.86 μg m^?3, with an average concentration of 52.51 μg m^?3, which accounted for 82.5% of total elements. The concentrations of organic carbon and elemental carbon were 7.71 and 1.52 μg m^?3, respectively, lower than those before and after the meeting. It is indicated that during the meeting, limiting motor vehicles is to reduce exhaust emissions, delay heating is to reduce the fossil fuel combustion, and other measures are to reduce the concentration of PM_2.5. The directly dispersing by mixing layerheight increase and the indirectly reducing the formation of secondary aerosol by low relative humidity, andthese are the only two key removing mechanisms of PM_2.5 in Xinxiang during the meeting.     

Application of microcosm and species sensitivity distribution approaches in the ecological hazard assessment of 4-tert-butylphenol

In order to evaluate the ecological hazard of 4-tert-butylphenol (4-TBP), species abundances and physicochemical properties were monitored for 63 days in a microcosm system containing planktonic algae, rotifers, shrimps and Daphnia. The 63 days-NOEC (no observed effect concentration) of 4-TBP for this system was calculated. At the same time, species sensitivity distribution curves were constructed based on the toxicity data of EC₁₀, EC₅₀ and NOEC derived from laboratory single-species toxicity tests, which further gives no obvious hazard concentrations for 95% species in the ecosystem (HC₅). In both the microcosm and the single-species tests, the shrimp (Neocaridina sp.) was the most sensitive species to 4-TBP exposure, while most algae species were relatively insensitive compared to the zooplankton. For the microcosm exposed to 4-TBP, significant changes occurred to the community structure instead of the community function, resulting in a NOEC_microcosm of 265.38?μg?L^–1 which approached the EC₁₀-based HC₅ (0.376?mg?L^–1). Nevertheless, EC₅₀-based HC₅ was higher than the NOEC_microcosm, and the NOEC-based HC₅ was lower. The data showed that the EC₁₀-based HC₅ was protective at the similar level with the result of microcosm for 4-TBP, providing supportive data for chemical risk assessment.     

Estimating marine biogeochemical rates of the carbonate pH system—A Kalman filter tested

Oxygen (O₂), nitrate (NO₃), dissolved inorganic carbon (DIC) or pCO₂, and pH or total alkalinity (TA), are useful indices of marine chemical, physical and biological processes operating on varying time-scales. Although these properties are increasingly being monitored at high frequency, they have not been extensively used for studying ecosystem dynamics. We test whether we can estimate time-evolving biogeochemical rates (e.g. primary production, respiration, calcification and carbonate dissolution, and nitrification) from synthetic high frequency time-series of O₂, NO₃, DIC, pCO₂, TA or pH. More specifically, a Kalman filter has been implemented in a very simplified biogeochemical model describing the dynamics of O₂, NO₃, DIC and TA and linking the concentration data to biogeochemical fluxes. Different sets of concentration data are assimilated and biogeochemical rates are estimated. The frequency of assimilation required to get acceptable results is investigated and is compared with the frequency of sampling in the field or in controlled experimental settings.Smoothing of the data to remove data noise before assimilation improves the estimation of the biogeochemical rates. The best estimated rates are obtained when assimilating O₂, NO₃ and TA although the assimilation of DIC instead of TA also gives satisfactory results. In case pH or pCO₂ is assimilated rather than DIC or TA, the linearization of the (now nonlinear) observation equation introduces perturbations and the Kalman filter behaves suboptimal. We conclude that, given the resolution of data required, the tool has potential to estimate biogeochemical rates of the carbonate system under controlled settings.     

A kinetic study of phenol nitration and nitrosation with nitrous acid in the dark

We studied the transformation of phenol in the presence of nitrous acid in the dark. The main detected intermediates were 2-nitrophenol, 4-nitrophenol and 4-nitrosophenol. For the first time a kinetic analysis of the reaction in a pH interval relevant to environmental chemistry has been carried out. The kinetic data are consistent with phenol transformation being initiated by HNO₂. The results are relevant to the chemistry of the atmosphere, where HNO₂ forms upon heterogeneous conversion of ^·NO₂, and to water treatment techniques.     

Evidence for a new mechanism of Fe2O3 decomposition in lightweight aggregate formation

Hematite (Fe₂O₃) chemical reduction into FeO and Fe₃O₄ by releasing O₂ at high temperatures is considered one of the generally accepted mechanisms for processing waste minerals and clay into lightweight aggregate construction materials. In many case studies, this mechanism has not been strictly confirmed. To verify whether hematite can effectively release O₂ at 1,000–1,260°C, a material containing hematite, simulating waste sediments from a Taiwanese reservoir, was shaped into pellets and fired into lightweight aggregates at high temperatures for 20 min and studied with various techniques. As revealed by the X-ray absorption near-edge structure technique, almost all the hematite remained as Fe(III) in the pellets when fired at 1,000–1,260°C, implying a negligible release of O₂ leading to the creation of pores. This finding shows that the generally accepted mechanism for lightweight aggregate formation associated with hematite decomposition into FeO, Fe₃O₄, and O₂ is invalid. Furthermore, Fe(III)-containing composites were formed in the fired pellets. Although firing at 1,000°C can trigger the decomposition of the components K₂CO₃, Na₂CO₃, and CaCO₃ with a release of CO₂, the sintering reaction was seemingly too weak to encapsulate the gases effectively. For pellets fired at 1,050–1,150°C, pores grew in size because the sintering reaction sufficed to generate a glassy phase that could better encapsulate gases.     

Toxic metal health risk by mussel consumption

Seafood is a major dietary food worldwide. However, seafood consumption by humans can induce health risk because seafood may be contaminated by various pollutants. The mussel Mytilus galloprovincialis is widely distributed in the coastal waters of Montenegro, SouthEast Adriatic Sea. Here, Zn, Fe, Cu, Ni, Cd, Pb, As, and Hg contents in M. galloprovincialis from ten sites were analyzed to investigate health risks associated with the consumption of wild and cultivated mussels. Since there is a lack of data on the mussel consumption rate in Montenegro, the amount of mussels that can be ingested weekly over a lifetime with no risk of negative health effects was calculated using provisional tolerable weekly intakes (PTWI). We found that Cd concentrations were the limiting factor for mussels as a food. The weekly consumptions of 0.64–1.2 kg of fresh wild and 0.84–1.2 kg of fresh cultivated mussel would be sufficient to reach the PTWI_Cd, which may result in a risky weekly intake of Cd for long-term exposure. Moreover, weekly intake of 125 g mussels was used to calculate the dietary intake of trace elements by mussel consumption and compared with the prescribed PTWIs. Here, we found that there is no risk for human health for all investigated elements. In this case, the highest Cd level obtained in wild and in cultivated mussels represents 19.8 and 14.9% of the PTWI_Cd, respectively. This is the first study in Montenegro giving an assessment of the health risk from trace elements via the consumption of wild and cultivated M. galloprovincialis.     

Comparison of sample digestion procedures for the determination of trace elements in antarctic krill by GF‐AAS

Two independent digestion procedures for Antarctic krill samples were compared. Dry ashing (DA) and microwave (MW) acid‐assisted digestion were tested for decomposing the samples to determine essential (Cu, Fe, Cr) and toxic elements (Cd, Pb) by graphite furnace‐atomic absorption spectrometry (GF‐AAS). A mixture of HNO₃ and H₂O₂ as digesting agent was used in the microwave procedure. For the dry ashing digestion, the organic matter was oxidated at 480°C in an open system. Both digestion methods were compared in terms of accuracy and applied to the analysis of a certified reference material: MURST‐ISS‐A2 (Antarctic krill).

The detection limits for the five elements analysed ranged from 3 to 150 ng g^‐1. Both digestion procedures are suitable for the decomposition of krill samples. However, dry ashing is not recommended to determine Pb and Cd because losses can occur.     

Effects of interpolation and data resolution on methane emission estimates from rice paddies

Rice paddies are an important source of the greenhouse gas methane (CH₄). Global methane emission estimates are highly uncertain and do not account for effects of interpolation or data resolution errors. This paper determines such scaling effects for the influence of soil properties on calculated CH₄ emissions for the island of Java, Indonesia. The effects of different interpolation techniques, variograms and neighbor optimization were tested for soil properties by cross-validation. Interpolated organic carbon values were not significantly different from the original soil samples, in contrast to interpolated soil iron contents. Interpolation of soil properties coupled to a process-based model on CH₄emissions led to a significant change in distribution of calculated CH₄ emissions, i.e., the variance decreased. Effects of data resolution were examined by interpolating soil properties to derive data at different data resolutions and then calculating CH₄ emissions by applying the process-based model at these resolutions. The soil properties did not differ significantly for different data resolutions, in contrast to calculated CH₄ emissions. These scaling effects were caused by the combination of interpolation and a non-linear model. Real scaling effects may even be larger because small-scale variability was not accounted for. Scaling effects, including those caused by small-scale variability, have to be considered to achieve unbiased and less uncertain global CH₄emissions estimates from rice paddies.     

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.     

Assessment of sulfurous springs in the west of Iraq for balneotherapy,drinking, irrigation and aquaculture purposes

This research deals with the sulfurous spring waters flow along the course of the Euphrates River in western Iraq in the area extended between Haqlaniya and Hit within the Al-Anbar governorate. Eleven springs (3 in Haqlanya, 4 in Kubaysa and 4 in Hit) have been addressed for the purpose of water evaluation for balneology, drinking, irrigation and aquaculture (fish farming). In order to meet the objectives of this research, all springs were sampled and analyzed for the total dissolved solid, electrical conductivity, pH, temperature, major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺), major anions (SO₄ ^2?, Cl^?, HCO₃ ^? and CO₃ ^2?), minor anions (PO₄ ^3?and NO₃ ^?) as well as the trace elements that included Pb, Zn, Cd, Ni, Fe, Mn, Cu, Br, F, Ba, B, Sr, Al, As, Cr, Hg and Se. The International Standards of World Health Organization are used for assessing the water quality. The results revealed that the springs belong to the tepid springs of 27–30 °C and classified as hypothermal to the thermal springs. Lithochemistry and geochemical processes clearly affected the water chemistry. The hydrogeochemical processes are responsible for the element enrichment in water by the chemical dissolution of carbonate and gypsum and evaporation as well. The results of the study indicate the possibility of using spring water for therapeutic purposes, but not allowed for drinking and aquaculture (fish farming), except those free of H₂S gas. On the other hand, it can be used for irrigation with risk. However, soil type as well as proper selection of plants should be taken into consideration.     

Effects of La3+, Ce3+ on nitrogen removal in sequencing batch reactor

Batch experiments were conducted to study the short-term biological effects of rare earth ions (La³⁺, Ce³⁺) and their mixture on the nitrogen removal in a sequencing batch reactor (SBR). The data showed that higher NH₄ ⁺-N removal rate, total inorganic nitrogen removal efficiency, and denitrification efficiency were achieved at lower concentrations of rare earth elements (REEs) (<1 mg/L). In the first hour of the aeration stage of SBR, the presence of REEs increased the total inorganic nitrogen removal efficiency and NH₄ ⁺-N removal efficiency by 15.7% and 10%–15%, respectively. When the concentrations of REEs were higher than 1 mg/L, the total inorganic nitrogen removal efficiency decreased, and nitrate was found to accumulate in the effluent. When the concentrations of REEs was up to 50.0 mg/L, the total inorganic nitrogen removal efficiency was less than 30% of the control efficiency with a high level of nitrate. Lower concentrations of REEs were found to accelerate the nitrogen conversion and removal in SBR.     

Synthetischer Crandallit

Crandallite (Ca,Sr) Al₃ (PO₄)₂ (OH)₅ · H₂O crystallizes in the alunitecrystal lattice. Because of its open structure, the cations Ca²⁺, Sr²⁺, and Al³⁺ can be replaced by various elements depending on their diadochial properties; the element entering into the crystal network thus becomes immobilized. Artificial amorphous crandallite has been shown to eliminate the heavy metal ions: Pb²⁺>>Cu²⁺>Hg²⁺>>Cd²⁺ from contamined water in the presence of lateritic phosphates. Pb²⁺ could be removed nearly quantitatively in all cases.     

Multivariate statistical techniques for the evaluation of spatial and temporal variations in water quality of the Mahanadi river–estuarine system (India) – a case study

Spatial and temporal distributions of water quality using multivariate statistical techniques for the evaluation of nutrients (NO₂-N, NO₃-N, NH₄-N, PO₄-P, SiO₄-Si, total N, total P) in relation to some physico-chemical features (DO, BOD, TSS, TDS, SO₄²⁻, Cl⁻) were studied for 31 different stations of the Mahanadi river–estuarine system in the eastern part of India. The seasonal nutrient variations (except SiO₄-Si) exhibit higher values during monsoon season in unpolluted stations and the reverse trends for polluted stations, which are related to agricultural run-off and regional anthropogenic activities respectively. Silicate shows a well defined pattern of distribution with a higher concentration during the monsoon, which is slightly removed from the estuarine water of Mahanadi during the pre-monsoon season. The results of R-mode factor analyses revealed that anthropogenic contributions are responsible for the increase in nutrients and the decrease in DO and pH levels of the water. The magnitude of BOD with respect to total N and P demonstrates the intensity of organic pollution in the system. The removal of silicate in the saline system is clearly visible through factor analysis and the different mode of association of TSS is reflected seasonally. The relationships among the stations are highlighted by cluster analysis, represented in dendograms to categorize different levels of contamination.     

The role of sample preparation in interpretation of trace element concentration variability in moss bioindication studies

Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO₃, H₂O₂) samples of two moss species (Hylocomium splendens and Pleurozium schreberi) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements’ geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations.     

An assessment of the air pollution data from two monitoring stations in Kuwait

This article assesses the air pollution data from two monitoring stations in Kuwait. The measurements cover major pollutants, i.e., CO, CO₂, methanated and non-methanated hydrocarbons, NO _x , SO₂, O₃, and particulate matter (PM10). The data also includes meteorological parameters, i.e., solar intensity, temperature, wind speed, and wind direction, and has been collected over a period 4 years, from 2001 to 2004. Data analysis includes the assessment of annual hourly averages and 1-h maxima. Typical pollutant concentration trends, similar to those previously reported for Kuwait and for other locations around the world, are observed except for particulate matter measurements, which have higher values because of proximity to the desert. Emissions of nitrogen oxides show a consistent increase over the years. This is caused by the increase in the number of motor vehicles and the expansion in power generation and industrial activities. The data collected is a subset of the air quality criteria, as defined by the US EPA (United States Environmental Protection Agency).