Determination of potentially toxic heavy metals in traditionally used medicinal plants for HIV/AIDS opportunistic infections in Ngamiland District in Northern Botswana

The determination of four potentially toxic heavy metals, arsenic, chromium, lead and nickel in twelve plant species used for the treatment of perceived HIV and AIDS-associated opportunistic infections by traditional healers in Ngamiland District in Northern Botswana, a metal mining area, was carried out using atomic absorption spectrometry. The medicinal plants; Dichrostachys cinerea, Maerua angolensis, Mimusops zeyheri, Albizia anthelmintica, Plumbago zeylanica, Combretum imberbe, Indigofera flavicans, Clerodendrum ternatum, Solanum panduriforme, Capparis tomentosa, Terminalia sericea and Maytenus senegalensis contained heavy metals in varying quantities: arsenic 0.19–0.54 μg g⁻¹, chromium 0.15–1.27 μg g⁻¹, lead 0.12–0.23 μg g⁻¹ and nickel 0.09–0.21 μg g⁻¹ of dry weight. Chromium was found to be the most abundant followed by arsenic and lead. Nickel was undetectable in nine plant species. M. senegalensis contained the largest amounts of arsenic, chromium and lead. All metals determined were below the WHO permissive maximum levels. The possible maximum weekly intakes of the heavy metals following treatment regimes were insignificant compared to the provisional tolerable weekly intake levels recommended by WHO and the Joint FAO/WHO Expert Committee on Food Additives. This suggests that heavy metal exposure to patients originating from consumption of traditional medicinal plant preparations is within non health-compromising limits.     

Simultaneous determination of trace arsenic(III), antimony(III), total arsenic and antimony in Chinese medicinal herbs by hydride generation-double channel atomic fluorescence spectrometry

A new method was developed for simultaneous determination of trace arsenic and antimony in Chinese herbal medicines by hydride generation-double channel atomic fluorescence spectrometry with a Soxhlet extraction system and an n-octanol-water extraction system, respectively. The effects of analytical conditions on the fluorescence intensity were investigated and optimized. A water-dissolving and methanol-water-dissolving capability were compared. The contents of different species in five Chinese herbal medicines and their decoctions were analyzed. The concentration ratios of n-octanol-soluble As or Sb to water-soluble As or Sb were related to the kinds of medicine and the acidity of the decoction. Soxhlet extraction was found to be an effective method for plants pretreatment for determination of arsenic and antimony species in Chinese herbs; the interferences of coexisting ions were evaluated. The proposed method has the advantages of simple operation, high sensitivity and high speed, with 3σ detection limits of 0.094 μg g⁻¹ for As(III), 0.056 μg g⁻¹ for total As, 0.063 μg g⁻¹ for Sb(III) and 0.019 μg g⁻¹ for total Sb in a 1.0 g of the sample.     

Eggshell membrane-based solid-phase extraction combined with hydride generation atomic fluorescence spectrometry for trace arsenic(V) in environmental water samples

The eggshell membrane (ESM) contains several surface functional groups such as amines, amides and carboxylic groups with potential as SPE adsorbent for the retention of target species of interest. In this paper, the potential use of ESM, a typical biomaterial, as solid-phase extraction (SPE) adsorbent is evaluated for analysis of trace arsenic(V) in environmental water samples in combination with hydride generation atomic fluorescence spectrometry (HG-AFS). In order to obtain the satisfactory recovery of arsenic(V), various parameters including the desorption and enrichment conditions such as pH, the flow rate and the volume of sample solution, the amount of ESM and the content of sodium chloride were systematically optimized and the effects of co-existed ions were also investigated in detail. Under the optimal conditions, arsenic(V) could be easily extracted by the ESM packed cartridge and the breakthrough adsorption capacity was found to be 3.9 μg g⁻¹. The favorable limit of detection (LOD) for arsenic(V) was found to be 0.001 μg L⁻¹ with an enrichment factor of 33.3, and the relative standard deviations (R.S.Ds) was 2.1% for 0.6 μg L⁻¹ arsenic (n = 11). The reproducibility among columns was satisfactory (R.S.D. among columns is less than 5%). The proposed method has been successfully applied to analysis of arsenic(V) in aqueous environmental samples, which suggests the ESM can be an excellent SPE adsorbent for arsenic(V) pretreatment and enrichment from real water samples.     

A microwave-assisted sequential extraction of water and dilute acid soluble arsenic species from marine plant and animal tissues

This paper describes the use of dilute nitric acid for the extraction and quantification of arsenic species. A number of extractants (e.g. water, 1.5 M orthophosphoric acid, methanol-water and dilute nitric acid) were tested for the extraction of arsenic from marine biological samples, such as plants that have proved difficult to quantitatively extract. Dilute 2% (v/v) nitric acid was found to give the highest recoveries of arsenic overall and was chosen for further optimisation. The optimal extraction conditions for arsenic were 2% (v/v) HNO₃, 6 min⁻¹, 90 °C. Arsenic species were found to be stable under the optimised conditions with the exception of the arsenoriboses which degraded to a product eluting at the same retention time as glycerol arsenoribose. Good agreement was found between the 2% (v/v) HNO₃ extraction and the methanol-water extraction for the certified reference material DORM-2 (AB 17.1 and 16.2 μg g⁻¹, respectively, and TETRA 0.27 and 0.25 μg g⁻¹, respectively), which were in close agreement with the certified concentrations of AB 16.4 ± 1.1 μg g⁻¹ and TETRA 0.248 ± 0.054 μg g⁻¹.To preserve the integrity of arsenic species, a sequential extraction technique was developed where the previously methanol-water extracted pellet was further extracted with 2% (v/v) HNO₃ under the optimised conditions. Increases in arsenic recoveries between 13% and 36% were found and speciation of this faction revealed that only inorganic and simple methylated species were extracted.     

Enzyme-assisted extraction and liquid chromatography mass spectrometry for the determination of arsenic species in chicken meat

Chicken is the most consumed meat in North America. Concentrations of arsenic in chicken range from μg kg⁻¹ to mg kg⁻¹. However, little is known about the speciation of arsenic in chicken meat. The objective of this research was to develop a method enabling determination of arsenic species in chicken breast muscle. We report here enzyme-enhanced extraction of arsenic species from chicken meat, separation using anion exchange chromatography (HPLC), and simultaneous detection with both inductively coupled plasma mass spectrometry (ICPMS) and electrospray ionization tandem mass spectrometry (ESIMS). We compared the extraction of arsenic species using several proteolytic enzymes: bromelain, papain, pepsin, proteinase K, and trypsin. With the use of papain-assisted extraction, 10 arsenic species were extracted and detected, as compared to 8 detectable arsenic species in the water/methanol extract. The overall extraction efficiency was also improved using a combination of ultrasonication and papain digestion, as compared to the conventional water/methanol extraction. Detection limits were in the range of 1.0–1.8 μg arsenic per kg chicken breast meat (dry weight) for seven arsenic species: arsenobetaine (AsB), inorganic arsenite (As^III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), inorganic arsenate (As^V), 3-nitro-4-hydroxyphenylarsonic acid (Roxarsone), and N-acetyl-4-hydroxy-m-arsanilic acid (NAHAA). Analysis of breast meat samples from six chickens receiving feed containing Roxarsone showed the presence of (mean ± standard deviation μg kg⁻¹) AsB (107 ± 4), As^III (113 ± 7), As^V (7 ± 2), MMA (51 ± 5), DMA (64 ± 6), Roxarsone (18 ± 1), and four unidentified arsenic species (approximate concentration 1–10 μg kg⁻¹).     

Feasibility of ultra-high performance liquid and gas chromatography coupled to mass spectrometry for accurate determination of primary and secondary phthalate metabolites in urine samples

Phthalates (PAEs) are ubiquitous toxic chemical compounds. During the last few years, some phthalate metabolites (MPAEs) have been proposed as appropriate biomarkers in human urine samples to determine PAE human intake and exposure. So, it is necessary to have fast, easy, robust and validated analytical methods to determine selected MPAEs in urine human samples. Two different instrumental methods based on gas (GC) and ultra-high performance liquid (UHPLC) chromatography coupled to mass spectrometry (MS) have been optimized, characterized and validated for the simultaneous determination of nine primary and secondary phthalate metabolites in urine samples. Both instrumental methods have similar sensitivity (detection limits ranged from 0.03 to 8.89 pg μL⁻¹ and from 0.06 to 0.49 pg μL⁻¹ in GC–MS and UHPLC–MS², respectively), precision (repeatability, expressed as relative standard deviation, which was lower than 8.4% in both systems, except for 5OH-MEHP in the case of GC–MS) and accuracy. But some advantages of the UHPLC–MS² method, such as more selectivity and lower time in the chromatographic runs (6.8 min vs. 28.5 min), have caused the UHPLC–MS² method to be chosen to analyze the twenty one human urine samples from the general Spanish population. Regarding these samples, MEP showed the highest median concentration (68.6 μg L⁻¹), followed by MiBP (23.3 μg L⁻¹), 5cx-MEPP (22.5 μg L⁻¹) and MBP (19.3 μg L⁻¹). MMP (6.99 μg L⁻¹), 5oxo-MEHP (6.15 μg L⁻¹), 5OH-MEHP (5.30 μg L⁻¹) and MEHP (4.40 μg L⁻¹) showed intermediate levels. Finally, the lowest levels were found for MBzP (2.55 μg L⁻¹). These data are within the same order of magnitude as those found in other similar populations.     

Determination of arsenic(III) and total inorganic arsenic in water samples using an on-line sequential insertion system and hydride generation atomic absorption spectrometry

A simple and robust on-line sequential insertion system coupled with hydride generation atomic absorption spectrometry (HG-AAS) was developed, for selective As(III) and total inorganic arsenic determination without pre-reduction step. The proposed manifold, which is employing an integrated reaction chamber/gas-liquid separator (RC-GLS), is characterized by the ability of the successful managing of variable sample volumes (up to 25 ml), in order to achieve high sensitivity. Arsine is able to be selectively generated either from inorganic As(III) or from total arsenic, using different concentrations of HCl and NaBH₄ solutions. For 8 ml sample volume consumption, the sampling frequency is 40 h⁻¹. The detection limit is c_L = 0.1 and 0.06 μg l⁻¹ for As(III) and total arsenic, respectively. The precision (relative standard deviation) at 2.0 μg l⁻¹ (n = 10) level is s_r = 2.9 and 3.1% for As(III) and total arsenic, respectively. The performance of the proposed method was evaluated by analyzing the certified reference material NIST CRM 1643d and spiked water samples with various concentration ratios of As(III) to As(V). The method was applied for arsenic speciation in natural waters samples.     

Method development for the determination of cadmium in fertilizer samples using high-resolution continuum source graphite furnace atomic absorption spectrometry and slurry sampling

The determination of cadmium (Cd) in fertilizers is of major interest, as this element can cause growth problems in plants, and also affect animals and humans. High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with charge-coupled device (CCD) array detection overcomes several of the limitations encountered with conventional line source AAS, especially the problem of accurate background measurement and correction. In this work an analytical method has been developed to determine Cd in fertilizer samples by HR-CS GF AAS using slurry sampling. Both a mixture of 10 μg Pd + 6 μg Mg in solution and 400 μg of iridium as permanent modifier have been investigated and aqueous standards were used for calibration. Pyrolysis and atomization temperatures were 600 °C and 1600 °C for the Pd-Mg modifier, and 500 °C and 1600 °C for Ir, respectively. The results obtained for Cd in the certified reference material NIST SRM 695 (Trace Elements in Multi-Nutrient Fertilizer) of 16.7 ± 1.3 μg g⁻¹ and 16.4 ± 0.75 μg g⁻¹ for the Pd-Mg and Ir modifier, respectively, were statistically not different from the certified value of 16.9 ± 0.2 μg g⁻¹ on a 95% confidence level; however, the results obtained with the Ir modifier were significantly lower than those for the Pd-Mg modifier for most of the samples. The characteristic mass was 1.0 pg for the Pd-Mg modifier and 1.1 pg Cd for the Ir modifier, and the correlation coefficients (R²) of the calibration were > 0.99. The instrumental limits of detection were 7.5 and 7.9 ng g⁻¹, and the limits of quantification were 25 and 27 ng g⁻¹ for Pd-Mg and Ir, respectively, based on a sample mass of 5 mg. The cadmium concentration in the investigated samples was between 0.07 and 5.5 μg g⁻¹ Cd, and hence below the maximum value of 20 μg g⁻¹ Cd permitted by Brazilian legislation.     

Determination of inorganic arsenic species in natural waters—Benefits of separation and preconcentration on ion exchange and hybrid resins

A simple method for the separation and determination of inorganic arsenic (iAs) species in natural and drinking water was developed. Procedures for sample preparation, separation of As(III) and As(V) species and preconcentration of the total iAs on fixed bed columns were defined. Two resins, a strong base anion exchange (SBAE) resin and a hybrid (HY) resin were utilized. The inductively-coupled plasma-mass spectrometry method was applied as the analytical method for the determination of the arsenic concentration in water. The governing factors for the ion exchange/sorption of arsenic on resins in a batch and a fixed bed flow system were analyzed and compared. Acidity of the water, which plays an important role in the control of the ionic or molecular forms of arsenic species, was beneficial for the separation; by adjusting the pH values to less than 8.00, the SBAE resin separated As(V) from As(III) in water by retaining As(V) and allowing As(III) to pass through. The sorption activity of the hydrated iron oxide particles integrated into the HY resin was beneficial for bonding of all iAs species over a wide range of pH values from 5.00 to 11.00. The resin capacities were calculated according to the breakthrough points in a fixed bed flow system. At pH 7.50, the SBAE resin bound more than 370 μg g⁻¹ of As(V) while the HY resin bound more than 4150 μg g⁻¹ of As(III) and more than 3500 μg g⁻¹ of As(V). The high capacities and selectivity of the resins were considered as advantageous for the development and application of two procedures, one for the separation and determination of As(III) (with SBAE) and the other for the preconcentration and determination of the total arsenic (with HY resin). Methods were established through basic analytical procedures (with external standards, certified reference materials and the standard addition method) and by the parallel analysis of some samples using the atomic absorption spectrometry-hydride generation technique. The analytical properties of both procedures were similar: the limit of detection was 0.24 μg L⁻¹, the limit of quantification was 0.80 μg L⁻¹ and the relative standard deviations for samples with a content of arsenic from 10.00 to 300.0 μg L⁻¹ ranged from 1.1 to 5.8%. The interference effects of anions commonly found in water and some organic species which can be present in water were found to be negligible. Verification with certified reference materials proved that the experimental concentrations found for model solutions and real samples were in agreement with the certified values.     

Accurate determination of trace amounts of phosphorus in geological samples by inductively coupled plasma atomic emission spectrometry with ion-exchange separation

In order to determine trace amounts of phosphorus in geological and cosmochemical rock samples, simple as well as reliable analytical schemes using an ICP-AES instrument were investigated. A (conventional) ICP-AES procedure could determine phosphorus contents at the level of several 100 μg g⁻¹ with a reasonable reproducibility (<10% for 200 μg g⁻¹; 1σ). An ICP-AES procedure coupled with matrix-separation using cation and anion exchange resins could lower the quantification level down to 1 μg g⁻¹ or even lower under the present experimental conditions. The matrix-separation ICP-AES procedure developed in this study was applied to twenty-one geological reference samples issued by Geological Survey of Japan. Obtained values vary from 1250 μg g⁻¹ for JB-3 (basalt) to 2.07 μg g⁻¹ for JCt-1 (carbonate). Matrix-separation ICP-AES yielded reasonable reproducibility (less than 8.3%; 1σ) of three replicate analyses for all the samples analyzed. In comparison of our data with certificate values as well as literature or reported values, there appear to be an apparent (and large) discrepancy between our values and certificate/reported values regardless of phosphorus contents. Based on the reproducibility of our data and the analytical capability of the matrix-separation ICP-AES procedure developed in this study (in terms of quantification limit, recovery, selectivity of an analyte through pre-concentration process, etc.), it is concluded that certified values for several reference standard rocks should be reevaluated and revised accordingly. It may be further pointed that some phosphorus data reported in literatures should be critically evaluated when they are to be referred in later publications.     

Speciation of inorganic arsenic in a sequential injection dual mini-column system coupled with hydride generation atomic fluorescence spectrometry

The separation and speciation of inorganic arsenic(III) and arsenic(V) are facilitated by employing a novel sequential injection system incorporating two mini-columns followed by detection with hydride generation atomic fluorescence spectrometry. An octadecyl immobilized silica mini-column is used for selective retention of the complex between As(III) and APDC, while the sorption of As(V) is readily accomplished by a 717 anion exchange resin mini-column. The retained As(III)-PDC complex and As(V) are effectively eluted with a 3.0 mol L⁻¹ hydrochloric acid solution as stripping reagent, which well facilitates the ensuing hydride generation process via reaction with tetrahydroborate. With a sampling volume of 1.0 mL and an eluent volume of 100 μL for both species, linear ranges of 0.05-1.5 μg L⁻¹ for As(III) and 0.1-1.5 μg L⁻¹ for As(V) are obtained, along with enrichment factors of 7.0 and 8.2, respectively. Precisions of 2.8% for As(III) and 2.9% for As(V) are derived at the concentration level of 1.0 μg L⁻¹. The practical applicability of the procedure has been demonstrated by analyzing a certified reference material of riverine water (SLRS-4), in addition to spiking recovery in a lake water sample matrix.     

Determination of octylphenol and nonylphenol in aqueous sample using simultaneous derivatization and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A simple and fast sample preparation method for the determination of nonylphenol (NP) and octylphenol (OP) in aqueous samples by simultaneous derivatization and dispersive liquid–liquid microextraction (DLLME) was investigated using gas chromatography–mass spectrometry (GC/MS). In this method, a combined dispersant/derivatization catalyst (methanol/pyridine mixture) was firstly added to an aqueous sample, following which a derivatization reagent/extraction solvent (methyl chloroformate/chloroform) was rapidly injected to combine in situ derivatization and extraction in a single step. After centrifuging, the sedimented phase containing the analytes was injected into the GC port by autosampler for analysis. Several parameters, such as extraction solvent, dispersant solvent, amount of derivatization reagent, derivatization and extraction time, pH, and ionic strength were optimized to obtain higher sensitivity for the detection of NP and OP. Under the optimized conditions, good linearity was observed in the range of 0.1–1000 μg L⁻¹ and 0.01–100 μg L⁻¹ with the limits of detection (LOD) of 0.03 μg L⁻¹ and 0.002 μg L⁻¹ for NP and OP, respectively. Water samples collected from the Pearl River were analyzed with the proposed method, the concentrations of NP and OP were found to be 2.40 ± 0.16 μg L⁻¹ and 0.037 ± 0.001 μg L⁻¹, respectively. The relative recoveries of the water samples spiked with different concentrations of NP and OP were in the range of 88.3–106.7%. Compared with SPME and SPE, the proposed method can be successfully applied to the rapid and convenient determination of NP and OP in aqueous samples.     

Application of multivariate techniques in the optimization of a procedure for the determination of bioavailable concentrations of Se and As in estuarine sediments by ICP OES using a concomitant metals analyzer as a hydride generator

A procedure has been developed for the determination of bioavailable concentrations of selenium and arsenic in estuarine sediments employing inductively coupled plasma optical emission spectrometry (ICP OES) using a concomitant metals analyzer device to perform hydride generation. The optimization of hydride generation was done in two steps: using a two-level factorial design for preliminary evaluation of studied factors and a Doehlert design to assess the optimal experimental conditions for analysis. Interferences of transition metallic ions (Cd²⁺, Co²⁺, Cu²⁺, Fe³⁺ and Ni²⁺) to selenium and arsenic signals were minimized by using higher hydrochloric acid concentrations. In this way, the procedure allowed the determination of selenium and arsenic in sediments with a detection limit of 25 and 30 μg kg⁻¹, respectively, assuming a 50-fold sample dilution (0.5 g sample extraction to 25 mL sample final volume). The precision, expressed as a relative standard deviation (% RSD, n = 10), was 0.2% for both selenium and arsenic in 200 μg L⁻¹ solutions, which corresponds to 10 μg g⁻¹ in sediment samples after acid extraction. Applying the proposed procedure, a linear range of 0.08-10 and 0.10-10 μg g⁻¹ was obtained for selenium and arsenic, respectively. The developed procedure was validated by the analysis of two certified reference materials: industrial sludge (NIST 2782) and river sediment (NIST 8704). The results were in agreement with the certified values. The developed procedure was applied to evaluate the bioavailability of both elements in four sediment certified reference materials, in which there are not certified values for bioavailable fractions, and also in estuarine sediment samples collected in several sites of Guanabara Bay, an impacted environment in Rio de Janeiro, Brazil.     

Mass spectrometric profiling of saturated fatty acid esters of steroids separated by high-temperature gas chromatography

An efficient analytical method for simultaneous determination of 12 SFEs in serum is described. The method involves solid-phase extraction to isolate of SFEs from interfering species, especially cholesteryl esters, conversion to trimethylsilyl (TMS) ether derivatives for the direct analysis by gas chromatography–mass spectrometry (GC–MS) using a high temperature MXT-1 (Silcosteel-treated stainless steel) capillary column. All SFEs as their TMS derivatives were well separated with excellent peak shapes within 12 min. Overall recoveries ranged from 88% to 119%, with a detection limits for SFEs ranged from 2 to 30 μg L⁻¹. The linearity as correlation coefficient was higher than 0.99 except for pregnenolone-3-arachidate (r² = 0.98) in the concentration range of 5–3000 μg L⁻¹. Ten serum samples obtained from volunteers were also analyzed and quantitatively determined of DHEA-3-palmitate and pregnenolone-3-stearate in 1.8–1195.8 μg L⁻¹ concentration. The devised high temperature GC–MS method could be useful for identification of SFEs in biological specimens including serum.     

Concentration levels of total and methylmercury in mussel samples collected along the coasts of Sardinia Island (Italy)

This paper reports the assessment of the total mercury (T-Hg) and methylmercury (MeHg) contamination of mussel samples collected by two sampling campaigns from along the coastline of Sardinia (Italy). T-Hg has been determined by a direct mercury analyser (DMA) whereas MeHg has been determined by gas chromatography-mass spectrometry (GC-MS) after acid extraction, and employs a novel NaBPh₄ derivatization method. The evaluation of the quality of measurements was carried out by analysing candidate certified reference material (CRM) BCR 710, for MeHg and T-Hg, and CRM IAEA-350 for T-Hg. In the analysed samples, the T-Hg concentrations range from 35 to 115 μg kg⁻¹ and from 40 to 830 μg kg⁻¹, for the two sampling campaigns, respectively, whereas the MeHg concentrations range from l5 to 51 μg kg⁻¹ and from 17 to 116 μg kg⁻¹. Consequently, the MeHg/T-Hg ratios range from 0.33 to 0.91 and from 0.14 to 0.98, respectively. Despite the increasing trend of Hg concentration from the first to the second sampling campaign, the T-Hg concentration of all the samples was much below the 0.5 μg g⁻¹ WHO limit, and the MeHg values ranged between 2.2 and 17.2 μg kg⁻¹, not exceeding the 43.5 μg kg⁻¹ tolerable daily residue level calculated for Italy.     

Measurement of methyl mercury (I) and mercury (II) in fish tissues and sediments by HPLC-ICPMS and HPLC-HGAAS

A procedure for the extraction and determination of methyl mercury and mercury (II) in fish muscle tissues and sediment samples is presented. The procedure involves extraction with 5% (v/v) 2-mercaptoethanol, separation and determination of mercury species by HPLC-ICPMS using a Perkin-Elmer 3 μm C8 (33 mm × 3 mm) column and a mobile phase 3 containing 0.5% (v/v) 2-mercaptoethanol and 5% (v/v) CH₃OH (pH 5.5) at a flow rate 1.5 ml min⁻¹ and a temperature of 25 °C. Calibration curves for methyl mercury (I) and mercury (II) standards were linear in the range of 0-100 μg l⁻¹ (r² = 0.9990 and r² = 0.9995 respectively). The lowest measurable mercury was 0.4 μg l⁻¹ which corresponds to 0.01 μg g⁻¹ in fish tissues and sediments. Methyl mercury concentrations measured in biological certified reference materials, NRCC DORM - 2 Dogfish muscle (4.4 ± 0.8 μg g⁻¹), NRCC Dolt - 3 Dogfish liver (1.55 ± 0.09 μg g⁻¹), NIST RM 50 Albacore Tuna (0.89 ± 0.08 μg g⁻¹) and IRMM IMEP-20 Tuna fish (3.6 ± 0.6 μg g⁻¹) were in agreement with the certified value (4.47 ± 0.32 μg g⁻¹, 1.59 ± 0.12 μg g⁻¹, 0.87 ± 0.03 μg g⁻¹, 4.24 ± 0.27 μg g⁻¹ respectively). For the sediment reference material ERM CC 580, a methyl mercury concentration of 0.070 ± 0.002 μg g⁻¹ was measured which corresponds to an extraction efficiency of 92 ± 3% of certified values (0.076 ± 0.04 μg g⁻¹) but within the range of published values (0.040-0.084 μg g⁻¹; mean ± s.d.: 0.073 ± 0.05 μg g⁻¹, n = 40) for this material. The extraction procedure for the fish tissues was also compared against an enzymatic extraction using Protease type XIV that has been previously published and similar results were obtained. The use of HPLC-HGAAS with a Phenomenox 5 μm Luna C18 (250 mm × 4.6 mm) column and a mobile phase containing 0.06 mol l⁻¹ ammonium acetate (Merck Pty Limited, Australia) in 5% (v/v) methanol and 0.1% (w/v) l-cysteine at 25 °C was evaluated as a complementary alternative to HPLC-ICPMS for the measurement of mercury species in fish tissues. The lowest measurable mercury concentration was 2 μg l⁻¹ and this corresponds to 0.1 μg g⁻¹ in fish tissues. Analysis of enzymatic extracts analysed by HPLC-HGAAS and HPLC-ICPMS gave equivalent results.     

Optimization of a GFAAS method for determination of total inorganic arsenic in drinking water

The new 10 μg l⁻¹ arsenic standard in drinking water has been a spur to the search for reliable routine analytical methods with a limit of detection at the μg l⁻¹ level. These methods also need to be easy to handle due to the routine analyses that are required in drinking water monitoring. Graphite furnace atomic absorption spectrometry (GFAAS) meets these requirements, but the limit of detection is generally too high except for methods using a pre-concentration or separation step. The use of a high-intensity boosted discharge hollow-cathode lamp decreases the baseline noise level and therefore allows a lower limit of detection. The temperature program, chemical matrix modifier and thermal stabilizer additives were optimized for total inorganic arsenic determination with GFAAS, without preliminary treatment. The optimal furnace program was validated with a proprietary software. The limit of detection was 0.26 μg As l⁻¹ for a sample volume of 16 μl corresponding to 4.2 pg As. This attractive technique is rapid as 20 samples can be analysed per hour. This method was validated with arsenic reference solutions. Its applicability was verified with artificial and natural groundwaters. Recoveries from 91 to 105% with relative standard deviation <5% can be easily achieved. The effect of interfering anions and cations commonly found in groundwater was studied. Only phosphates and silicates (respectively at 4 and 20 mg l⁻¹) lead to significant interferences in the determination of total inorganic arsenic at 4 μg l⁻¹.     

Sensitive determination of hydrazine in water by gas chromatography–mass spectrometry after derivatization with ortho-phthalaldehyde

A gas chromatography–mass spectrometric (GC–MS) method has been established for the determination of hydrazine in drinking water and surface water. This method is based on the derivatization of hydrazine with ortho-phthalaldehyde (OPA) in water. The following optimum reaction conditions were established: reagent dosage, 40 mg mL⁻¹ of OPA; pH 2; reaction for 20 min at 70 °C. The organic derivative was extracted with methylene chloride and then measured by GC–MS. Under the established condition, the detection and the quantification limits were 0.002 μg L⁻¹ and 0.007 μg L⁻¹ by using 5.0-mL of surface water or drinking water, respectively. The calibration curve showed good linearity with r² = 0.9991 (for working range of 0.05–100 μg L⁻¹) and the accuracy was in a range of 95–106%, and the precision of the assay was less than 13% in water. Hydrazine was detected in a concentration range of 0.05–0.14 μg L⁻¹ in 2 samples of 10 raw drinking water samples and in a concentration range of 0.09–0.55 μg L⁻¹ in 4 samples of 10 treated drinking water samples.     

Coacervative microextraction ultrasound-assisted back-extraction technique for determination of organophosphates pesticides in honey samples by gas chromatography–mass spectrometry

Coacervative microextraction ultrasound-assisted back-extraction technique (CME-UABE) is proposed for the first time for extracting and preconcentrating organophosphates pesticides (OPPs) from honey samples prior to gas chromatography–mass spectrometry (GC–MS) analysis. The extraction/preconcentration technique is supported on the micellar organized medium based on non-ionic surfactant. To enable coupling the proposed technique with GC, it was required to back extract the analytes into hexane. Several variables including, surfactant type and concentration, equilibration temperature and time, matrix modifiers, pH and buffers nature were studied and optimized over the relative response of the analytes. The best working conditions were as follows: an aliquot of 10 mL 50 g L⁻¹ honey blend solution was conditioned by adding 100 μL 0.1 mol L⁻¹ hydrochloric acid (pH 2) and finally extracted with 100 μL Triton X-114 100 g L⁻¹ at 85 °C for 5 min using CME technique. Under optimal experimental conditions, the enrichment factor (EF) was 167 and limits of detection (LODs), calculated as three times the signal-to-noise ratio (S/N = 3), ranged between 0.03 and 0.47 ng g⁻¹. The method precision was evaluated over five replicates at 1 ng g⁻¹ with RSDs ≤9.5%. The calibration graphs were linear within the concentration range of 0.3–1000 ng g⁻¹ for chlorpirifos; and 1–1000 ng g⁻¹ for fenitrothion, parathion and methidathion, respectively. The coefficients of correlation were ≥0.9992. Validation of the methodology was performed by standard addition method at two concentration levels (2 and 20 ng g⁻¹). The recoveries were ≥90%, indicating satisfactory robustness of the methodology, which could be successfully applied for determination of OPPs in honey samples of different Argentinean regions. Two of the analyzed samples showed levels of methidathion ranged between 1.2 and 2.3 ng g⁻¹.     

Automatic flow system for the sequential determination of copper in serum and urine by flame atomic absorption spectrometry

In this work, a fully automated flow system exploiting the advantages of the association of multi-pumping, multicommutation, binary sampling and merging zones, to accomplish the sequential determination of copper in serum and urine by flame atomic absorption spectrometry, is described. The developed flow system allowed multiple tasks, such as serum samples preparation (samples and standard solutions viscosity adjustment), serum copper (SCu) measurement, urine copper (UCu) pre-concentration and its subsequent elution and measurement, to be carried out sequentially. The implemented flow manifold presented a modular configuration consisting on two quasi-independent modules, each one accountable for a specific sample manipulation and whose combined operation under computer control enabled the determination of copper in a wide concentrations range.Once optimised and with a sample consumption of about 0.250 mL of serum and 7 mL of urine, the developed flow system allowed linear calibration plots up to 5 mg L⁻¹ with a detection limit of 0.035 mg L⁻¹ for SCu and linear calibration plots up to 300 μg L⁻¹ with a detection limit of 0.67 μg L⁻¹ for UCu. The sampling rate varied according to the module employed and was about 360 determinations h⁻¹ (SCu module), 12 determinations h⁻¹ (UCu module) or 24 determinations h⁻¹ (12 urine and 12 serum samples; UCu and SCu modules simultaneously). Repeatability studies (R.S.D.%, n = 10) showed good precision for UCu at concentrations of 25 μg L⁻¹ (2.54%), 50 μg L⁻¹ (0.90%) and 100 μg L⁻¹ (1.62%) as well as for SCu at concentrations of 0.25 mg L⁻¹ (8.11%), 1 mg L⁻¹ (3.11%) and 5 mg L⁻¹ (0.90%). A comparative evaluation showed a good agreement between the results obtained in the analysis of UCu and SCu (n = 18) by both the developed methodology and the reference procedures. Accuracy was further evaluated by means of the analysis of reference samples (Seronorm™ Trace Elements Urine and Seronorm™ Trace Elements Serum) and the obtained results complied with the certified values.