Electroanalytical and chromatographic determination of pentachlorophenol and related molecules in a contaminated soil: a real case example

Electroanalytical and chromatographic methodologies have been applied for the determination of pentachlorophenol (PCP) and some of its derivatives in real soil samples contaminated by industrial discharge. The analytes were extracted with hexane from soil samples collected at different points of the site and mixed to produce a representative sample. Square wave voltammetry (SWV) experiments were carried out on either a boron-doped diamond (BDD) electrode or a gold ultramicroelectrode (Au-UME) in an analyte composed by the Britton-Robinson (B-R) buffer at pH 5.5 with the direct addition of proper amounts of the extract. The voltammetric responses revealed an irreversible anodic peak at approximately 0.80 V vs. Ag/AgCl with a peak current showing a linear dependence on PCP concentration. This linear relationship yielded a detection limit (DL) of 2×10⁻⁸ mol l⁻¹ (or 5.5 μg l⁻¹) for the BDD electrode and 6.9×10⁻⁸ mol l⁻¹ (18.4 μg l⁻¹) for the Au-UME, while the independently measured HPLC detection limit was 1.1×10⁻⁸ mol l⁻¹ (3.0 μg l⁻¹). The application of electroanalytical and chromatographic methodologies in the analysis of soil extracts revealed, besides the PCP responses, signals for some related molecules such as o-tetrachlorobenzoquinone (o-chloranil), hexachlorobenzene and tetrachlorophenol. Recovering experiments for PCP showed a concentration of 27.5 mg kg⁻¹ for the electroanalytical determinations and 26.8 mg kg⁻¹ for the HPLC analysis, values exceedingly high if considering that the maximum residue limit established for natural waters by the Brazilian Environmental Agency is 10 μg l⁻¹.     

Insight into the extractability of metals from soils using an implementation of the linear adsorption isotherm model

This paper deals with an often overlooked artifact in sequential and single extraction of metals from soils, viz. the volume to mass (V/m) ratio as a potential source for inadequate extraction yields. We offer a theoretical framework to get a grip on this intricate parameter and came up with a model based on a linear adsorption isotherm to derive the correct maximal metal extractability for a certain extractant. We verified the model experimentally using 0.1 mol l⁻¹ nitric acid for extraction of seven metals (Cr, Co, Cu, Cd, Pb, Ni and Zn) from an urban soil sample, and concluded that commonly used V/m ratios in the range of 10-40 ml g⁻¹ may give as much as 50% too low extraction yields. Thus, a strong caveat is in place as to be very critical what V/m ratios to use and preferably apply the model derived to obtain the correct maximal extractability using a variable V/m ratio method.     

Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS

Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the ⁶⁴Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched ⁶⁵Cu stable isotope and measurement of ⁶³Cu/⁶⁵Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of ⁶³Cu/⁶⁵Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils.     

Development of a simple extraction and clean-up procedure for determination of organochlorine pesticides in soil using gas chromatography–tandem mass spectrometry

A procedure based on QuEChERS extraction and a simultaneous liquid–liquid partition clean-up was developed. The procedure involved extraction of hydrated soil samples using acetonitrile and clean-up by liquid–liquid partition into n-hexane. The hexane extracts produced were clean and suitable for determination using gas chromatography–tandem mass spectrometry (GC–MS/MS). The method was validated by analysis of soil samples, spiked at five levels between 1 and 200 μg kg⁻¹. The recovery values were generally between 70 and 100% and the relative standard deviation values (%RSDs) were at or below 20%. The procedure was validated for determination of 19 organochlorine (OC) pesticides. These were hexachlorobenzene (HCB), α-HCH, β-HCH, γ-HCH, heptachlor, heptachlor epoxide (trans), aldrin, dieldrin, chlordane (trans), chlordane (cis), oxychlordane, α-endosulfan, β-endosulfan, endosulfan sulfate, endrin, p,p′-DDT, o,p′-DDT, p,p′-DDD and p,p′-DDE. The method achieved low limits of detection (LOD; typically 0.3 μg kg⁻¹) and low limits of quantification (LOQ; typically 1.0 μg kg⁻¹). The method performance was also assessed using five fortified soil samples with different physico-chemical properties and the method performance was consistent for the different types of soil samples. The proposed method was compared with an established procedure based on Soxtec extraction. This comparison was carried out using six soil samples collected from regions of Pakistan with a history of intensive pesticide use. The results of this comparison showed that the two procedures produced results with good agreement. The proposed method produced cleaner extracts and therefore led to lower limits of quantification. The proposed method was less time consuming and safer to use. The six samples tested during this comparison showed that soils from cotton growing regions contained a number of persistent OC residues at relatively low levels (<10 μg kg⁻¹). These residues were α-HCH, γ-HCH, heptachlor, chlordane (trans), p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, β-endosulfan and endosulfan sulfate.     

Application of a quick,easy, cheap,effective, rugged and safe-based method for the simultaneous extraction of chlorophenols,alkylphenols, nitrophenols and cresols in agricultural soils,analyzed by using gas chromatography–triple quadrupole-mass spectrometry/mass spectrometry

Due to the different physico-chemical properties of phenols, the development of a methodology for the simultaneous extraction and determination of phenolic compounds belonging to several families, such as chlorophenols (CPs), alkylphenols (APs), nitrophenols (NTPs) and cresols is difficult. This study shows the development and validation of a method for the analysis of 13 phenolic compounds (including CPs, APs, NTPs and cresols) in agricultural soils. For this purpose, a quick, easy, cheap, effective, rugged and safe (QuEChERS)-based procedure was developed, validated and applied to the analysis of real samples. A derivatization step prior to the final determination by gas chromatography (GC) coupled to a triple quadrupole analyzer operating in tandem mass spectrometry (QqQ-MS/MS) was performed by using acetic acid anhydride (AAA) and pyridine (Py). The optimized procedure was validated, obtaining average extraction recoveries in the range 69–103% (10 μg kg⁻¹), 65–98% (50 μg kg⁻¹), 76–112% (100 μg kg⁻¹) and 76–112% (300 μg kg⁻¹), with precision values (expressed as relative standard deviation, RSD) ≤ 22% (except for 4-chlorophenol) involving intra-day and inter-day studies. Furthermore, 15 real soil samples were analyzed by the proposed method in order to assess its applicability. Some phenolic compounds (e.g. 2,4,6-trichlorophenol or 4-tert-octylphenol) were found in the samples at trace levels (<10 μg kg⁻¹).     

Comparison of two laser-induced breakdown spectroscopy techniques for total carbon measurement in soils

The potentials of two advanced laser-induced breakdown spectroscopy (LIBS) techniques which are used to determine the total carbon content in soils have been examined. The first one is the combination of a single-pulse laser ablation with spark excitation of plasma plume triggering the gap between electrodes close to the target surface. The second one is a more conventional double-pulse LIBS. In both modes the calibration graphs have a nonlinear trend in the actual range of carbon contents and present a good R² value (0.97). In the combined laser-spark approach, using low-cost and portable laser instrumentation is possible, as well as inducing a micro-damage on the target surface. Certain regularities in the spectral line intensities of soil nutritious elements have been detected and appear to be connected to the total carbon content and to the soil origin.     

Environmental biodegradation of synthetic polymers I. Test methodologies and procedures

Biodegradation of synthetic polymers is an important property that is used in many applications. Evaluation of the extent of biodegradation has used different methods in recent years. For each environmental compartment, different approaches have to be made in order to obtain valuable data on biodegradability.This review describes validated and accepted methods based on standardized biodegradation tests, analytical tests, enzymatic tests or tests of physical properties to evaluate the biodegradability of synthetic polymers for different types of environmental compartments (e.g., soil, compost or aqueous media).Part II of this review will subsequently report on the environmental biodegradation of different groups of synthetic polymers.     

A simplified version of the total kjeldahl nitrogen method using an ammonia extraction ultrasound-assisted purge-and-trap system and ion chromatography for analyses of geological samples

The total Kjeldahl nitrogen (TKN) method was simplified by using a manifold connected to a purge-and-trap system immersed into an ultrasonic (US) bath for simultaneous ammonia (NH₃) extraction from many previously digested samples. Then, ammonia was collected in an acidic solution, converted to ammonium (NH₄⁺), and finally determined by ion chromatography method. Some variables were optimized, such as ultrasonic irradiation power and frequency, ultrasound-assisted NH₃ extraction time, NH₄⁺ mass and sulfuric acid concentration added to the NH₃ collector flask. Recovery tests revealed no changes in the pH values and no conversion of NH₄⁺ into other nitrogen species during the irradiation of NH₄Cl solutions with 25 or 40 kHz ultrasonic waves for up to 20 min. Sediment and oil free sandstone samples and soil certified reference materials (NCS DC 73319, NCS DC 73321 and NCS DC 73326) with different total nitrogen concentrations were analysed. The proposed method is faster, simpler and more sensitive than the classical Kjeldahl steam distillation method. The time for NH₃ extraction by the US-assisted purge-and-trap system (20 min) was half of that by the Kjeldahl steam distillation (40 min) for 10 previously digested samples. The detection limit was 9 μg g⁻¹ N, while for the Kjeldahl classical/indophenol method was 58 μg g⁻¹ N. Precision was always better than 13%. In the proposed method, carcinogenic reagents are not used, contrarily to the indophenol method. Furthermore, the proposed method can be adapted for fixed-NH₄⁺ determination.     

Laboratory intercomparison study on the analysis of short-chain chlorinated paraffins in an extract of industrial soil

Short-chain chlorinated paraffins (SCCPs) comprise a class of organic pollutants used in many industrial applications and released into the environment. The analytical determination of SCCPs is very challenging. Although there is at present no fully validated measurement procedure that might be applied in routine monitoring, the European Union Water Framework Directive (WFD) has required regular monitoring of this class of compounds at river-basin scale since 2007.To assess the status quo of the analysis of SCCPs in relation to the requirements of the WFD, we organized an interlaboratory comparison on the quantification of SCCPs in an extract of an industrial soil. Six laboratories participated in the exercise using three different techniques [i.e. gas chromatography (GC) coupled to mass spectrometry (MS) in electron-capture negative ionization mode, GC with atomic emission detection, and carbon-skeleton GC-MS]. The results reported were in the range 8.5–3200 mg/L. This confirms that reliable quantification of SCCPs is still very difficult to achieve and that the comparability of SCCP data reported to the European Commission is at least questionable.     

Recent advances in the environmental applications of biosurfactants

Biosurfactants can be used for heavy metal or organic contaminant removal from contaminated soil or for bioremediation enhancement. Most research has been performed on the use of rhamnolipids. However, present and future studies involve new biosurfactants and new applications as sustainable, renewable additives for nanoparticle production and use.