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.     

In-situ electrochemical measurements of total concentration and speciation of heavy metals in acid mine drainage (AMD): assessment of the use of anodic stripping voltammetry

We assessed the use of anodic stripping voltammetry (ASV) for in-situ determinations of both total concentration and speciation of dissolved heavy metals (Cd, Cu, Pb and Zn) in acid mine drainage (AMD). In the Kwangyang Au–Ag mine area of South Korea, different sites with varying water chemistry within an AMD were studied with a field portable anodic stripping voltammeter. Anodic stripping voltammetry after wet oxidation (acidification) was very sensitive enough to determine total concentration of dissolved Cd because Cd was dominantly present as ‘labile’ species, whilst the technique was not so effective for determining total Cu especially in the downstream sites from the retention pond, due to its complexation with organic matter. For dissolved Pb, the concentrations determined by ASV after wet oxidation generally agreed with those by ICP-AES. In the downstream samples (pH>5), however, ASV data after wet oxidation were lower than ICP-AES data because a significant fraction of dissolved Pb was present in those samples as ‘inert’ species associated with colloidal iron oxide particles. The determination of total dissolved Zn by ASV after wet oxidation appeared to be unsatisfactory for the samples with high Cu content, possibly due to the interference by the formation of Zn–Cu intermetallic compounds on the mercury coated electrode. In AMD samples with high dissolved iron, use of ultraviolet irradiation was not effective for determining total concentrations because humate destruction by UV irradiation possibly resulted in the removal of a part of dissolved heavy metals from waters through the precipitation of iron hydroxides.     

Effects of daily nickel intake on the bio-accumulation,body weight and length in tilapia (Oreochromis niloticus)

Nickel pollution is a serious environmental problem, and its effects may provoke alterations in the ecosystem and in organism of animals and humans. Dermatitis, eczema, and asthma are some illnesses caused by Ni²⁺ poisoning. In this work, fish fed either Ni²⁺-enriched pellets or commercial pellets were studied. The amount of Ni²⁺ in fish were measurements by adsorptive stripping voltammetry (AdSV) with dimethylglyoxime as a complexing agent. The analysis of Ni²⁺ in fish by AdSV established that its accumulation occurs principally in viscera (670.86 ± 5.82 µg g^?1), in the head (697.12 ± 2.77 µg g^?1) and in the muscle (405.82 ± 3.26 µg g^?1), both after 12 months of experiments. Ni²⁺ adsorbs preferentially in organs such as the stomach, the intestine, and the kidneys and acts in the central nervous system as well. Tilapia growth and mass were significantly affected by Ni²⁺ poisoning. From statistical analysis, observed that the results for lengths, weights and metal concentration were different for each sampling at significance level of p < 0.05. The Ni²⁺ concentration in tilapia was enough to cause the death of tilapias; however, it did not occur because the presence of Zn²⁺ might act as protective agent of heavy metals.     

A simple voltammetric procedure for speciation and evaluation of As removal from water

Here, we show a fast and sensitive method for the determination of inorganic arsenic in natural waters using differential pulse cathodic stripping voltammetry. All the arsenite determinations were done in 2.0 mol L⁻¹ HCl + 3.15 × 10⁻⁴ mol L⁻¹ Cu(II) supporting electrolyte. 1 × 10⁻³ mol L⁻¹ sodium thiosulphate was used as As(V) reducing agent. The detection limit was 0.5 μg L⁻¹ for both species. The method has been applied to water samples collected in an arsenic-contaminated region of Brazil, in particular, to verify the efficiency of the solar oxidation and removal of arsenic process applied to these waters.     

Chemistry and adsorption-desorption properties of manganese oxides deposited in Forehill Water Treatment Plant,Grampian, Scotland

Manganese oxide coatings on sand particles within filtration beds from a water treatment plant in Grampian, Scotland were examined to determine their control on metal mobility. This study first sought to characterise the oxides, notably their mineralogy and metal content, to provide a foundation for studies on the adsorption of dissolved metals from the treated water by the oxides. The oxides were examined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and analysed by flame atomic absorption spectrophotometry (AAS). These techniques showed the oxide coatings were amorphous but uniformly distributed over each sand grain. The oxides were selectively removed from the sand grains prior to analysis by AAS using a hydroxylamine hydrochloride selective leaching method. The compositional range of the extracts was 100–150 mg L⁻¹ Mn; 30–55 mg L⁻¹ Fe; 17–56 mg L⁻¹ Ca; 4.6–7.0 mg L⁻¹ Ni; 4.6–6.8 mg L⁻¹ Zn and 1.3–5.7 mg L⁻¹ Mg. When these results are expressed as mg of metal per mg of Mn, the metal content of the oxides is remarkably uniform: 0.25–0.37 mg Fe; 0.14–0.35 mg Ca; 0.035–0.042 mg Ni; 0.035–0.040 mg Zn; 0.01–0.04 mg Mg. The greatest metal concentrations were consistently found in the upper 3 cm of the filtration bed, and these decrease with increasing depth. After the beds are cleaned a more uniform distribution of metals occurs throughout the bed. The metals taken up by the manganese coating are retained over a wide pH range with the exception of Ca and Mg which desorb to a significant extent. The percentage of calcium and magnesium lost from the coating ranges from 30–94%, the amount being dependent on the final pH of the solution. The presence of manganese oxide in the filtration beds appears to be advantageous in terms of removal of transition metals from the treated water.     

Vanadium and molybdenum concentrations in particulate from Palermo (Italy): analytical methods using voltammetry

The main purpose of this work was to develop a reliable method for the determination of vanadium (V) and molybdenum (Mo) in atmosphere particles or aerosols because they can not be readily measured using conventional techniques. For this research, 30 particulate samples were collected from five different stations located at Palermo, Italy. We used the catalytic adsorptive stripping voltammetry and differential pulsed voltammetry to measure V and Mo in atmospheric particulate, respectively. The represented method includes advantages of high sensitivity, high selectivity, simplicity, reproducibility, speed and low costs. The quantification limits for V and Mo are, respectively, 0.57 and 0.80 ng·m⁻³. The precision, expressed as relative standard deviation (RSD %), was about 2% for both metals. The mean recoveries of added V and Mo were about 99.5% and ranged from 97% to 101%. Vanadium concentrations in particulate samples collected in Palermo area ranged from 0.57 to 7.7 ng·m⁻³, while Mo concentrations were in the range 0.8–51 ng·m⁻³. In many cases the concentrations of two elements in the particulate samples fall below the detection limits. The mean concentrations for V and Mo in particulate samples, collected in Palermo area, were respectively 3.1 and 5.9 ng·m⁻³.     

Pollution assessment of the lower basin of Lakes Kainji/Jebba, Nigeria: heavy metal status of the waters, sediments and fishes

The objective of this investigation was to examine the heavy metal status of the lower basin of Kainji dam (used for hydroelectricity generation), which includes Lakes Kainji/Jebba, Nigeria, and the potential for human exposure to heavy metals from eating fish caught in the lakes. Water, sediments and fish were sampled from the lakes and evaluated for As, Cu, Co, Cr, Fe, Hg, Mn, Ni, Pb, Sb, Ti, V and Zn using the EDXRF technique. Fe and Mn were found to be present at high mean concentrations in the water (13 and 9 μg L^-1), sediment (7092 and 376 μg g^-1) and fish (11.4 and 4.6 μg g^-1) samples. Sb (3.2 μg L^-1), Ti (4.1 μg L^-1), Cr (2.2 μg L^-1), Co (1.2 μg L^-1), Cu (1.3 μg L^-1) and Pb (1.2 μg L^-1) in the water samples and Sb (29 μg g^-1), Ti (27 μg g^-1), V (27 μg g^-1), Cr (27 μg g^-1), Co (40 μg g^-1), Ni (33 μg g^-1), Cu (25 μg g^-1), Zn (59 μg g^-1) and Pb (19 μg g^-1) in the sediment samples were found to be of medium mean concentrations. The other metals were present at trace levels (<1 μg), including As and Hg in the fish and sediment samples. There was an appreciable increase in␣metal concentrations in going from the water to the sediment samples. The probable source of the pollutants is anthropogenic, arising from agricultural activities, corrosion/abrasion of the ferrous steel material and additives in the lubricants and insulation used for auxiliary services on the turbine floor of the dam constructed on the lakes. However, natural geological sourcing from the underlying lake rock cannot be totally ignored, particularly the high levels of Fe and Mn in the sediment samples. The potential risk for human exposure to these metals emanates from the fish caught in the lakes and subsequently consumed, as there are already significant levels of these metals in the two fish species analysed, Tilapia (Oreochromis niloticus) and Chrysicthys (Chrysicthys auratus).     

Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Application of the electrochemical speciation of heavy metals in tracking groundwater pollution

The application of the electrochemical speciation of heavy metals in tracking groundwater is presented. Three fractions interchangeable, associated to the organic materials and associated to the matter in suspension of the metals Zn, Cd, Pb and Cu by means of the anodic stripping voltammetry were determined. The parameters of the determination were: electrodeposition potential ‐1.2 V, time of deaerating with nitrogen 300 s, time of the electrolysis 90 s (with stirring) and the rest time 40 s. The core of this work was to determine the validity of this scheme of electrochemical speciation in the pursuit of the follow‐up of groundwater pollution caused by heavy metals after the breakdown of the mining raft at the River Guadiamar Basin (Andalusia, Spain).     

Seasonal AVS–SEM relationship in sediments and potential bioavailability of metals in industrialized estuary, southeastern Brazil

In anoxic sediments, as those found in estuaries, the mobility of metals can be controlled by the formation of stable sulfide complexes. The potential bioavailability of a metal can then be predicted on the basis of the acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) criterion. Distributions of AVS and SEM (Hg, Cu, Pb, Cd, Zn, and Ni) along the sediment profiles were determined seasonally for three rivers that constitute the Santos-Cubat?o estuarine system (SE Brazil), which is located in one of the most industrialized areas of Latin America. AVS and SEM concentrations varied significantly, from 0.04 to 31.9 μmol g⁻¹ and 0.086–6.659 μmol g⁻¹, respectively. The highest AVS levels in sediments were detected in the winter, whereas high SEM values predominated in the summer. Considering SEM–AVS molar differences as a parameter to evaluate potential bioavailability, sediments nearest to the industrial area represent higher risk to biota, especially during the summer. It is due to relatively low AVS values and not necessarily high concentrations of metals.     

Risk to humans of consuming metals in anchovy (<Emphasis Type="Italic">Coilia</Emphasis> sp.) from the Yangtze River Delta

Concentrations of metals were determined in four species of anchovy (Coilia sp.) from the Yangtze River, Taihu Lake, and Hongze Lake in Jiangsu Province, China. Concentrations of Cr in anchovy fish muscle ranged from 2.6 × 10⁻² to 5.0 mg/kg ww, and Coilia nasus taihuensis in Jiaoshan, Taihu Lake contained the highest concentrations of Cr, which was almost 111-fold higher than the mean value at other locations. Concentrations of Pb ranged from 1.5 × 10⁻² to 1.3 × 10⁻¹ mg/kg ww. Comparisons of concentrations of lead (Pb) among the four species indicated that anadromous species contained higher concentrations of Pb than did freshwater species. However, concentrations of Pb in C. nasus from the Nanjing and Haimen locations in the Yangtze River were not significant higher than those of two freshwater species: C. nasus taihuensis from Taihu Lake and C. brachygnathus from Hongze Lake (Duncan’s test, α = 0.05). While concentrations of Cd and Zn ranged from 7.0 × 10⁻⁴ to 3.6 × 10⁻³ mg/kg ww and 3.4 to 4.8 mg/kg ww, respectively, there were no significant differences in concentrations among the eight locations. The only concentration of the metals studied that exceeded the Chinese National Standard was Cr in Coilia from Jiaoshan, Taihu Lake, which was 2.5-fold higher than the standard. These results indicate that people who consume the genus Coilia are not at risk due to concentrations of metals, except Cr in C. nasus taihuensis from Jiaoshan in Taihu Lake. Concentrations of all of the metals studied except for Cr were similar to or less than those of metals in most other areas in the world.     

Assessment of toxicity of heavy metal contaminated soils by the toxicity characteristic leaching procedure

The concentrations of Cu, Zn, Pb and Cd in soils near a lead–zinc mine located in Shangyu, Zhejiang Province, China, were determined and their toxicity was assessed using the toxicity characteristic leaching procedure (TCLP) developed by the United States Environmental Protection Agency. The TCLP method is a currently recognized international method for evaluation of heavy metal pollution in soils. The available levels of Cu, Zn, Pb and Cd were 8.2–36, 23–143, 6.4–1367 and 0.41–2.2 mg kg⁻¹, respectively, while the international standards were 15, 25, 5 and 0.5 mg kg⁻¹, respectively. Soils around the mine were more polluted with Zn and Pb, followed by Cd and Cu. Moreover, the levels of heavy metals in the soils extracted by TCLP indicated that extraction fluid 2 was more effective than extraction fluid 1 in extracting the heavy metals from the polluted soils and there was a positive correlation between fluids 1 and 2. Available heavy metal contents determined by TCLP were correlated with soil total heavy metal contents.     

Kinetic measurements of metal accumulation in two marine macroalgae

 We measured the uptake kinetics of four metals (Cd, Cr, Se and Zn) in two marine macroalgae (the green alga Ulva lactuca and the red alga Gracilaria blodgettii). Metal uptake generally displayed a linear pattern with increasing exposure time. With the exception of Cr, which exhibited comparable uptake rate constants at different concentrations, uptake rate constants of Cd, Se and Zn decreased with increasing metal concentration, indicating that the seaweeds had a higher relative uptake at lower metal concentration. Uptake of Cd and Zn was higher in U. lactuca than in G. blodgettii, whereas uptake of Cr and Se was comparable between the two species. Only Cd and Zn uptake in U. lactuca was significantly inhibited by dark exposure. A decrease in salinity from 28 to 10‰ enhanced the uptake of Cd, Cr, Se and Zn in U. lactuca 1.9-, 3.0-, 3.6-, and 1.9-fold, respectively. In G. blodgettii, Cd uptake increased twofold when salinity was decreased from 28 to 10‰, whereas uptake of Cr and Zn was not significantly affected by salinity change. The calculated depuration rate constants of metals in U. lactuca were 0.01 d⁻¹ for Cd, 0.05 to 0.08 d⁻¹ for Cr, 0.14 to 0.16 d⁻¹ for Se, and 0.12 to 0.15 d⁻¹ for Zn, and were relatively independent of the metal body burden in the algae. The predicted bioconcentration factor was 3 × 10⁴ for Cd, 2 × 10³ for Cr, 40 to 150 for Se, and 1 to 2 × 10⁴ for Zn in U. lactuca. Our kinetic study suggested that U. lactuca would be a good biomonitor of Cr and Zn contamination in coastal waters. Received: 14 September 1998 / Accepted: 29 May 1999     

Risk assessment of heavy metal contamination in shrimp farming in Mai Po Nature Reserve, Hong Kong

An ecological survey was carried out to determine the sediment concentrations of nutrients and heavy metals and bioaccumulation of heavy metals in fish and shrimp including tilapia (Oreochromis mossambicus×O. nilotica), grey mullet (Mugil cephalus), gei wai shrimp (Metapenaeus ensis) and caridean shrimp (Macrobrachium nipponensis) in the traditional tidal shrimp ponds (gei wais) of Mai Po Nature Reserve, Hong Kong. The sediments collected from the landward sites contained higher nutrient contents, as well as zinc (Zn), chromium (Cr), copper (Cu), nickel (Ni) and cadmium (Cd) than those collected from the seaward sites, but vice versa for lead (Pb) and mercury (Hg). However, the concentrations of all metals were exceptionally high in the two sites located outside the reserve, suggesting that waters from Deep Bay might be the possible source of metal contamination affecting the reserve. All metals studied seemed to accumulate in the viscera of fish. Body size was the determining factor for the accumulation of heavy metals in caridean shrimp and gei wai shrimp but not fish. Concentrations of the metals studied in tissues of grey mullet and gei wai shrimp were found to be safe for human consumption. Concentrations of Cr in tilapia whole body (0.68–1.10 mg kg⁻¹ wet weight) were close to or over the guideline value of 1 mg kg⁻¹ set by the Food Adulteration (Metallic Contamination) Regulations of Hong Kong. Tilapia flesh and small caridean shrimp collected from gei wais were contaminated by Cr and Pb but still fit for human consumption. Caution is required if large caridean shrimp is to be consumed in large amounts continuously because the concentration of Pb exceeded the maximum permitted concentration (6 mg kg⁻¹). The rather high Cr concentrations in tilapia whole body should not be overlooked as the fish will serve as a food source for migratory birds visiting the site.     

Some Preliminary Observations On Zinc and Cadmium Accumulative Capacity in Arum Italicum Mill

Pot and hydroponic trials as well as tests on samples collected in a mining area and in two different urban sites of Tuscany were carried out on Arum italicum Mill (Italian arum) plants. Zinc and cadmium contents were determined by differential pulse anodic stripping voltammetry (DPASV) in different organs of about 180 samples. After 65 days treatment, zinc and cadmium median contents in leaves of plants grown hydroponically in solutions containing both metals at different concentrations fell within the range of 281-2022 and 8.3-45.1 μg g^-1 (dry weight), respectively. Some Italian arum plants were also cultivated in pots in the presence or absence of malate or citrate in order to evaluate the role of these ligands in zinc and cadmium accumulation. Citrate enhanced cadmium uptake compared to malate.     

Single and combined effects of heavy metals and hormones on lysosomes of haemolymph cells from the mussel Mytilus galloprovincialis

Effects of heavy metals on lysosomes were studied in living cells from the mussel (Mytilus galloprovincialis Lam.). Haemolymph cells were obtained from the mussel adductor muscle, stained with neutral red (NR), and analysed by digital imaging to evaluate NR retention times within lysosomes. Exposure to Hg²⁺, Cd²⁺ and Cu²⁺ induced a reduction of NR retention time, indicating lysosomal membrane destabilisation. The intensity of these effects was correlated with the metal affinity for sulfhydryls. In contrast, Zn²⁺ showed no effect on lysosomes. Moreover, 200 μM Zn²⁺ protected lysosomes against the effects of Cd²⁺ and Cu²⁺, but not against Hg²⁺. Cell loading with the fluorescent pH probe Lyso Sensor followed by digital imaging showed a rise of lysosomal pH induced by Cd²⁺ and Hg²⁺, while Zn²⁺ prevented the effect of Cd²⁺ and also partially that of Hg²⁺. The different protective effect of Zn²⁺ against Hg²⁺ suggests a dual action of Hg²⁺ on lysosomes, possibly involving both membrane destabilisation and proton pump inhibition. Cell exposure to 17 β-estradiol also caused a reduction of NR retention time, which was synergistic to that of Hg²⁺. This suggests a common pathway between metals and hormone, possibly involving Ca²⁺ signaling. Received: 17 November 1999 / Accepted: 29 June 2000     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Heavy Metals in Epiphytic Mosses: An Experience in Florence

The epiphytic moss Hypnum cupressiforme has been used for passive monitoring of airborne heavy metals pollution by vehicular traffic in the urban area of Florence. Lead, cadmium, zinc and copper were determined by differential pulse anodic stripping voltammetry (DPASV). in the summer of 1993 about 30 samples were collected from the trunks of holm oak at the same height (1 metre) from the soil. Lead contents fall within the range of 0.02-1.08 μ moles g^-1 (dry weight) and for this metal, the emission source may be attributed mainly to vehicular traffic in poorly industrialized urban areas. Some evaluations have been carried out about the employment of Zn/Pb molar ratio for characterizing airborne pollution in urban areas.     

Concentrations of inorganic elements in 20 municipal waters in Sweden before and after treatment – links to human health

The water chemistry of 20 municipal water treatment plants in southern Sweden, representing various bedrock situations, and water qualities, were investigated. Four water samples, raw and treated, were collected from each plant and analyzed by predominantly ICP-OES and ICP-MS at four occasions from June to December, 2001. The concentrations of Ca, Mg, K, Na, HCO₃ and a number of micronutrients, varied considerably in treated waters from the studied plants (ranges; Ca: 9.1–53.7 mg L⁻¹, Mg: 1.4–10.9 mg L⁻¹, K: 1.1–4.8 mg L⁻¹, Na; 5.4–75.6 mg L⁻¹, HCO₃: 27–217 mg L⁻¹). The elimination of Fe and Mn from raw water was efficient in all treatments investigated, giving concentrations in treated waters below the detection limits at some plants. Softening filters gave waters with Ca-concentrations comparable to the softest waters in this study. Adjustment of pH by use of chemicals like lye, soda or lime, modified the consumer water composition significantly, besides raising the pH. It was estimated that drinking water contributed to approximately 2.2–13% of the daily Ca uptake, if the gastrointestinal uptake efficiency from food and water was estimated to be around 50%. The corresponding figures for Mg was 1.0–7% and for F 0–59%. None of the studied elements showed any significant time trends in raw or treated waters during the follow-up period. The concentrations of potentially toxic metals such as Al, Pb and U were low and did not indicate risks for adverse health effects (ranges; Al: 0.5–2.3 μg L⁻¹, Pb: 0–0.3 μg L⁻¹, U: 0.2.5 μg L⁻¹).