Development of a new analytical approach based on cellulose membrane and chelator for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L⁻¹ of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L⁻¹) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.     

New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu≅Fe≫Ni>Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS–metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.     

In situ differentiation of labile/inert metal species in Brazilian tropical rivers by means of a time-controlled batch-procedure based on TEPHA resin

The present study deals with a new analytical procedure based on a cellulose diffusion membrane and immobilised tetraethylene-pentamine-hexaacetate chelator (DM-TEPHA) for an in situ differentiation of labile and inert metal species in aquatic systems. The DM-TEPHA system was prepared by placing TEPHA chelator in pre-purified cellulose bags and in situ applied immersing the system in two Brazilian rivers to study the relative lability of metal species (Cu, Pb, Fe, Mn and Ni) as a function of the time and the quantity of exchanger, respectively. The procedure is simple and enables a new perspective for understanding the complexation, transport, stability and lability of metal species in aquatic systems rich in organic matter.     

Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: a review

This review provides a critical assessment of knowledge regarding the determination of organic phosphorus (OP) and organic nitrogen (ON) in aquatic systems, with an emphasis on biogeochemical considerations and analytical challenges. A general background on organic phosphorus and organic nitrogen precedes a discussion of sample collection, extraction, treatment/conditioning and preconcentration of organic phosphorus/nitrogen from sediments, including suspended particulate matter, and waters, including sediment porewaters. This is followed by sections on the determination of organic phosphorus/nitrogen components. Key techniques covered for organic phosphorus components are molecular spectrometry, atomic spectrometry and enzymatic methods. For nitrogen the focus is on the measurement of total organic nitrogen concentrations by carbon hydrogen nitrogen analysis and high temperature combustion, and organic nitrogen components by gas chromatography, high-performance liquid chromatography, gel electrophoresis, mass spectrometry, nuclear magnetic resonance spectrometry, X-ray techniques and enzymatic methods. Finally future trends and needs are discussed and recommendations made.     

Performance evaluation of two chelating ion-exchange sorbents for the fractionation of labile and inert metal species from aquatic media

The performance of two iminodiacetate chelating resins, applied in an element fractionation scheme, was investigated for the characterization of marine and stream water samples collected in potentially contaminated harbor and industrial zones. The comparison involved an evaluation of the sorption/desorption behavior of Cd, Cu, Pb and Zn on Chelex-100, a sorbent extensively employed for metal speciation studies, and on Lewatit TP-207, a material with similar chelating characteristics for which no applications for fractionation studies are reported. A characterization of the latter resin in terms of the influence of sample pH on the uptake of metals from aqueous solutions and their subsequent acid elution was carried out. Fractionation studies were performed on natural water samples and model solutions resembling their composition, spiked with micromolar concentrations of the metals. The operationally defined fractionation scheme is based on dynamic adsorption of the resin-labile fractions of metals on microcolumns made of the sorbents. This stage is followed by a batch procedure in which the eluent from the column is contacted with fresh resin to discriminate between the relatively stable species unable to react with the resin during the column interaction time, and the strongly complexed metals that do not interact with the sorbent even for periods of several hours. Results were obtained from coarsely filtered sub-samples and from specimens passed through membrane filters of pore size 0.45 and 0.22 µm. The method was also assessed with model solutions of the metals containing variable concentrations (in the 10^-3–10^-7 molar range) of complex forming agents such as nitrilotriacetic acid and trans-1,2-diaminocyclohexane-N,N,N,N-tetraacetic acid. An additional batch method, in which a fixed amount of resin was contacted with sample solution for increasing periods of time and the amount of metal remaining in solution measured as a function of the elapsed time, was used to obtain information on the kinetics of dissociation of species formed in the presence of added complexants. The behavior of both resins was similar, demonstrating that the discrimination of species derived from experiments with Chelex-100 may be properly validated by independent fractionation tests carried out with Lewatit TP-207. The behavior of the sorbents is also discussed in terms of the possible influence of particulate or colloidal materials and of kinetic effects related to the presence of complexing agents.     

Biomonitoring: an appealing tool for assessment of metal pollution in the aquatic ecosystem

Wide occurrence of aquatic metal pollution has caused much attention. Biomonitoring offers an appealing tool for the assessment of metal pollution in aquatic ecosystem. The bioindicators including algae, macrophyte, zooplankton, insect, bivalve mollusks, gastropod, fish, amphibian and others are enumerated and compared for their advantages and disadvantages in practical biomonitoring of aquatic metal pollution. The common biomonitoring techniques classified as bioaccumulation, biochemical alterations, morphological and behavior observation, population- and community-level approaches and modeling are discussed. The potential applications of biomonitoring are proposed to mainly include evaluation of actual aquatic metal pollution, bioremediation, toxicology prediction and researches on toxicological mechanism. Further perspectives are made for the biomonitoring of metal pollution in aquatic ecosystem.     

Validation and application of an analytical method for monomethylmercury quantification in aquatic plant tissues

An analytical methodology for monomethylmercury (MMHg) determination in aquatic plant tissues with low detection limit (346 pg g⁻¹) is proposed. It consists of acid digestion (HBr/CuSO₄), cleanup step with a Na₂S solution, pre-concentration procedure using a dithizone solution in toluene and quantification by GC–ECD. The performance of the methodology has been tested by determining the MMHg concentrations in the certified reference material Fucus Sea Plant Homogenate—IAEA-140/TM (CRM) and in leaves, stems and roots of the salt marsh plants Sarcocornia fruticosa and Halimione portulacoides. The results obtained for CRM were not statistically different ( = 0.056) from the certified value and repeatability was lower than 2.5% for the plant samples analyzed. This coefficient of variation was similar to those obtained in the externally quality control using within-batch and between-batch (<1.4%).     

Dissolution of cellulose in ionic liquids as a way to obtain test materials for metal-ion detection

Cellulose films containing entrapped analytical reagents suitable for metal-ion detection are produced by joint dissolution of cellulose and the reagents in ionic liquids then precipitation with water. The conditions of preparation of these test materials have been optimized and their properties have been studied. The film obtained by use of the ionic liquid 1-butyl-3-methylimidazolium chloride and 1-(2-pyridylazo)-2-naphthol has been used for colorimetric determination of divalent zinc, manganese, and nickel with detection limits at the 10⁻⁶ mol L⁻¹ level.     

Analytical methods for determination of free metal ion concentration, labile species fraction and metal complexation capacity of environmental waters: A review

Different experimental approaches have been suggested in the last few decades to determine metal species in complex matrices of unknown composition as environmental waters. The methods are mainly focused on the determination of single species or groups of species.The more recent developments in trace elements speciation are reviewed focusing on methods for labile and free metal determination.Electrochemical procedures with low detection limit as anodic stripping voltammetry (ASV) and the competing ligand exchange with adsorption cathodic stripping voltammetry (CLE-AdCSV) have been widely employed in metal distribution studies in natural waters. Other electrochemical methods such as stripping chronopotentiometry and AGNES seem to be promising to evaluate the free metal concentration at the low levels of environmental samples. Separation techniques based on ion exchange (IE) and complexing resins (CR), and micro separation methods as the Donnan membrane technique (DMT), diffusive gradients in thin-film gels (DGT) and the permeation liquid membrane (PLM), are among the non-electrochemical methods largely used in this field and reviewed in the text. Under appropriate conditions such techniques make possible the evaluation of free metal ion concentration.     

Development of the diffusive gradient in thin films technique for the measurement of labile mercury species in waters

The diffusive gradients in thin films (DGT) technique, utilizing resin gel with ion-exchange resin Duolite GT73 and new ion-exchange resin Ambersep GT74, was investigated for the accumulation of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, C₆H₅Hg⁺). The diffusion coefficients of mercury species in agarose gel calculated on the basis of Fick’s Law were mercury species-specific. The diffusion coefficients of Hg²⁺ and CH₃Hg⁺ at 25 °C (9.07 ± 0.23 × 10⁻⁶ cm² s⁻¹ and 9.06 ± 0.30 × 10⁻⁶ cm² s⁻¹, respectively) were very similar, but the diffusion coefficients of C₂H₅Hg⁺ (6.87 ± 0.23 × 10⁻⁶ cm² s⁻¹) and C₆H₅Hg⁺ (3.86 ± 0.19 × 10⁻⁶ cm² s⁻¹) were significantly lower. Influence of experimental conditions (pH, selected cations, chlorides and humic substance) on mercury species accumulation by DGT was studied. The DGT technique was applied to river water spiked with mercury species.     

Protonation constant of monoaza-12-crown-4 ether and stability constants with selected metal ions in aqueous solution in the presence of an excess of sodium ion: a potentiometric and differential pulse polarographic study at fixed ligand to metal ratio and varied pH

The ligand monoaza-12-crown-4 ether (A12C4) was studied in aqueous solution at 298 K and an ionic strength of 0.5 mol dm⁻³ in the presence of an excess of sodium ion (0.5 mol dm⁻³ NaNO₃). The protonation constant of A12C4, determined by glass electrode potentiometry (GEP) in the same background electrolyte, was found to be log K=9.36±0.03. Polarographic experimental and calculated complex formation curves (ECFC and CCFC) for labile metal–ligand systems, studied at a fixed total ligand (L_T) to total metal (M_T) concentration ratio and varied pH, were used for the modelling of the metal species formed and the refinement of their stability constants. The metal–ligand model and formation constants are optimised by solving mass-balance equations written for the assumed model and by fitting the CCFC to the ECFC. The CCFC can be generated for any metal–ligand model, including polynuclear metal species, for any L_T:M_T ratio, and for more than one ligand competing in the complex formation reaction. Three lead complexes with the ligand A12C4, viz. PbL²⁺, PbL(OH)⁺ and PbL(OH)₂, were found and their overall stability constants from differential pulse polarography (DPP), as log β, were estimated to be 3.75±0.03, 9.30±0.05 and 12.70±0.05, respectively. Two copper complexes CuL²⁺ and CuL(OH)₂ are reported and their stability constants (from DPP) were estimated to be 6.00±0.05 and 21.77±0.1, respectively. Two cadmium complexes CdL²⁺ and CdL(OH)⁺ are reported. The stability constant for CdL²⁺ was estimated from DPP and GEP as 2.80±0.05 and 2.68±0.03 (the latter value was obtained from a few potentiometric experimental points), respectively, and the stability constant for CdL(OH)⁺ from DPP was estimated to be 7.88±0.05. GEP could not be used for the stability constants determination of other metal complexes studied because of precipitation occurring prior the completion of a complex formation reaction.     

Lab-on-valve in the miniaturization of analytical systems and sample processing for metal analysis

In the past decade, the lab-on-valve (LOV) system, as the third-generation of the flow-injection analysis technique, has exhibited powerful capability in instrument miniaturization and on-line sample pretreatment.This review presents and discusses the state of the art in the progress of the LOV system in the determination of metal species in two parts:

•

miniaturization of analytical instrumentations; and,

•

sample-processing front-ends.

As a miniaturized analytical set-up, LOV incorporates detection techniques for the determination of metal species (e.g., spectrophotometry, electrochemical detection and atomic spectrometry). However, coupling LOV sample pretreatment with atomic or mass spectrometric detectors provides high-sensitivity determination or speciation of metal species.We also discuss future perspectives of the LOV system in metal determination and/or speciation.     

Hollow-fibre liquid phase microextraction for separation and preconcentration of vanadium species in natural waters and their determination by electrothermal vaporization-ICP-OES

For separation and determination of vanadium(IV/V) species, a fast and sensitive method by combining hollow-fibre liquid phase microextraction (HF-LPME) with electrothermal vaporization (ETV)-ICP-OES has been developed. Two vanadium species (V(IV) and V(V)) were separated by HF-LPME with the use of ammonium pyrrolidinecarbodithioate (APDC) as chelating agent for complexing with different V species and carbon tetrachloride as the extraction solvent, and the vanadium in the post-extraction organic phase was injected into the graphite furnace for ETV-ICP-OES detection, in which APDC was acted as the chemical modifier. At pH 5.0, both V(IV)-APDC and V(V)-APDC were extracted quantitatively into CCl₄ for determination of total V. For speciation studies, 1,2-cyclohexanediaminetetraacetic acid (CDTA) was added to the sample for masking V(IV), so that only V(V)-APDC was extracted and determined. The concentration of V(IV) was calculated by subtracting the V(V) concentration from the total concentration of V. Under the optimized experimental conditions, the enrichment factor was 74 and the detection limits for V(IV) and V(V) were 86 pg mL⁻¹ and 71 pg mL⁻¹, respectively. The proposed method has been applied to the speciation of V in environmental water samples, and the recovery was in the range of 94%-107%. The results show that V(V) is the dominant existence form in oxygenic water and V(IV) could not been detected. In order to validate the developed procedure, a NIES No.8 vehicle exhaust particulates certified reference material was analyzed, and the results obtained for total vanadium are in good agreement with the certified values. The proposed method is simple, rapid, selective, and sensitive and no oxidation/reduction is required, it is applicable to the speciation of vanadium in environmental samples with the complicated matrix.     

新型重金属离子捕集剂的合成及其对废水中铜离子的捕集作用

以活化硅胶为载体,γ-氯丙基三甲氧基硅烷为偶联剂,由乙二胺和二硫化碳合成了新型的具有螫合功能的氨基硫代甲酸聚合物(EPCR).研究了EPCR用量、pH值、反应时间、温度等对乙二胺四乙酸(EDTA)配合Cu2+溶液中Cu2+去除率的影响,确定了最佳去除条件.结果表明,EPCR对Cu2+的最大吸附量为34.10mmol/g...     

In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water

An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 °C for 60 min with 20% Na₂SO₄. The linear calibration curves were observed for the concentrations ranging from 1 to 300 μg L⁻¹ with the correlation coefficients (R²) being greater than 0.99. The method detection limits of most analytes were below 1 μg L⁻¹ except DCAA and MCAA that were 2 and 18 μg L⁻¹, respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water.     

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates. II. Evaluation of leachate treatment efficiency of different steps in a constructed pilot plant

Different methods for treatment of leachate from a municipal solid waste (MSW) landfill were tested in a pilot plant. Raw leachate was pre-treated with aeration and sedimentation, followed by several parallel individual steps such as bioremediation, chemical oxidation, ozonation, and geo-bed filters. The efficiency of different treatment steps was evaluated according to one previously developed protocol, which includes measurements of several parameters such as conductivity, pH, nutrients, chloride, metals, organic compounds, and acute toxicity before and after a treatment step. The treatment steps which showed the highest efficiency towards organic pollutants in leachate were ozone treatment and chemical oxidation. The use of an adsorption filter, a geo-bed with a mixture of peat and bottom ash with ca 10% remaining carbon, also had good effects. A combination of pre-treatment and a geo-bed filter with peat and carbon ash gave the best overall treatment results when water-quality parameters such as total organic carbon and ammonia-nitrogen were also considered.     

Development and application of an ultratrace method for speciation of organotin compounds in cryogenically archived and homogenized biological materials

An accurate, ultra-sensitive and robust method for speciation of mono, di, and tributyltin (MBT, DBT, and TBT) by speciated isotope-dilution gas chromatography-inductively coupled plasma-mass spectrometry (SID-GC-ICPMS) has been developed for quantification of butyltin concentrations in cryogenic biological materials maintained in an uninterrupted cryo-chain from storage conditions through homogenization and bottling. The method significantly reduces the detection limits, to the low pg g(-1) level (as Sn), and was validated by using the European reference material (ERM) CE477, mussel tissue, produced by the Institute for Reference Materials and Measurements. It was applied to three different cryogenic biological materials-a fresh-frozen mussel tissue (SRM 1974b) together with complex materials, a protein-rich material (whale liver control material, QC03LH03), and a lipid-rich material (whale blubber, SRM 1945) containing up to 72% lipids. The commutability between frozen and freeze-dried materials with regard to spike equilibration/interaction, extraction efficiency, and the absence of detectable transformations was carefully investigated by applying complementary methods and by varying extraction conditions and spiking strategies. The inter-method results enabled assignment of reference concentrations of butyltins in cryogenic SRMs and control materials for the first time. The reference concentrations of MBT, DBT, and TBT in SRM 1974b were 0.92 +/- 0.06, 2.7 +/- 0.4, and 6.58 +/- 0.19 ng g(-1) as Sn (wet-mass), respectively; in SRM 1945 they were 0.38 +/- 0.06, 1.19 +/- 0.26, and 3.55 +/- 0.44 ng g(-1), respectively, as Sn (wet-mass). In QC03LH03, DBT and TBT concentrations were 30.0 +/- 2.7 and 2.26 +/- 0.38 ng g(-1) as Sn (wet-mass). The concentration range of butyltins in these materials is one to three orders of magnitude lower than in ERM CE477. This study demonstrated that cryogenically processed and stored biological materials are a promising alternative to conventional freeze-dried materials for organotin speciation analysis, because these are, at present, the best conditions for minimizing degradation of thermolabile species and for long-term archival. Finally, the potential of the analytical method was illustrated by analysis of polar bear (Ursus maritimus) and beluga whale (Delphinapterus leuca) liver samples that had been collected in the Arctic and archived at the Marine Environmental Specimen Bank. Significant concentrations of butyltin compounds were found in the samples and provide the first evidence of the presence of this class of contaminant in the Arctic marine ecosystem. Figure Eye catch image.     

Monitoring and effects of nicosulfuron in aquatic mesocosms: development of a simple analytical procedure and evidence for low toxicity to phytoplankton communities

A new analytical procedure is proposed for monitoring nicosulfuron (sulfonylurea herbicide) in aquatic mesocosms derived from complex ecosystems. The approach is based on alternate use of the anionic and molecular forms of the pesticide during the procedure. It also takes into account the sensitivity of the molecule to hydrolysis. The procedure involves solid-phase extraction on a polystyrene–divinylbenzene support followed by a conventional high-performance liquid chromatographic analysis with UV-diode array detection. Recovery tests on samples from natural waters demonstrated that the performances obtained were convenient for monitoring aquatic mesocosms (recoveries of 91±12% at 0.5 g L^–1). The method was used to monitor nicosulfuron in mesocosms initially spiked at 2 or 30 g L^–1 . The evolution curves were compared to those obtained from mesocosms contaminated with atrazine at the same initial doses. The sensitivity of phytoplankton communities to nicosulfuron in aquatic mesocosms was found to be very limited.     

Development and validation of a quantitative method for the selective determination of tin species in tin octoate by differential pulse polarography

Tin octoate is used as a catalyst in the synthesis of polydimethylsiloxane (PDMS), a room temperature vulcanizing (RTV) silicone rubber. This rubber is largely used in the medical field due to its great biocompatibility. In this framework, a high-speed and costless analytical method for the determination of stannic ions, Sn(IV), in the presence of stannous ions, Sn(II), has been developed.The separation of these two ions was carried out using differential pulse polarography (DPP). For this purpose, the tin species contents in the catalyst is quantitatively extracted under inert condition to avoid any changes in the ratio Sn(IV)/Sn(II). Polarography showed well-shaped oxidation and reduction peaks respectively at −650 and −860 mV for stannous ions. The peak of the stannic ion was well separated and appeared at −1210 mV. Many parameters such as extraction process, extraction time, pH, chelating agents and polarographic conditions were optimized. We have also demonstrated that no oxidation of the stannous ions occurred during the sample preparation.The dosing range considered in this study extends between 10 and 40 μg/mL, corresponding to 6.8% and 27.2% of the degradation product (Sn(IV)) in the catalyst, regarding to the sampling. Finally this method was successfully validated using the total error concept.