A review of microplastic fibres: generation, transport, and vectors for metal(loid)s in terrestrial environments.

The laundering of synthetic fabrics has been identified as an important and diffuse source of microplastic (<5 mm) fibre contamination to wastewater systems. Home laundering can release up to 13 million fibres per kg of fabric, which end up in wastewater treatment plants. During treatment, 72-99% of microplastics are retained in the residual sewage sludge, which can contain upwards of 56 000 microplastics per kg. Sewage sludge is commonly disposed of by application to agricultural land as a soil amendment. In some European countries, application rates are up to 91%, representing an important pathway for microplastics to enter the terrestrial environment, which urgently requires quantification. Sewage sludge also often contains elevated concentrations of metals and metalloids, and some studies have quantified metal(loid) sorption onto various microplastics. The sorption of metals and metalloids is strongly influenced by the chemical properties of the sorbate, the solution chemistry, and the physicochemical properties of the microplastics themselves. Plastic-water partition coefficients for the sorption of cadmium, mercury and lead onto microplastics are up to 8, 32, and 217 mL g-1 respectively. Sorptive capacities of microplastics may increase over time, due to environmental degradation processes increasing the specific surface area and surface density of oxygen-containing functional groups. A range of metal(loid)s, including cadmium, chromium, and zinc, have been shown to readily desorb from microplastics under acidic conditions. Sorbed metal(loid)s may therefore become more bioavailable to soil organisms when the microplastics are ingested, due to the acidic gut conditions facilitating desorption. Polyester (polyethylene terephthalate) should be of particular focus for future research, as few quantitative sorption studies currently exist, it is potentially overlooked from density separation studies due to its high density, and it is by far the most widely used fibre in apparel textiles production.

Retardation of uranium and thorium by a cementitious backfill developed for radioactive waste disposal.

The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH)2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 µm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite.

The solubility of nickel and its migration through the cementitious backfill of a geological disposal facility for nuclear waste.

This work describes the solubility of nickel under the alkaline conditions anticipated in the near field of a cementitious repository for intermediate level nuclear waste. The measured solubility of Ni in 95%-saturated Ca(OH)2 solution is similar to values obtained in water equilibrated with a bespoke cementitious backfill material, on the order of 5×10(-7)M. Solubility in 0.02M NaOH is one order of magnitude lower. For all solutions, the solubility limiting phase is Ni(OH)2; powder X-ray diffraction and scanning transmission electron microscopy indicate that differences in crystallinity are the likely cause of the lower solubility observed in NaOH. The presence of cellulose degradation products causes an increase in the solubility of Ni by approximately one order of magnitude. The organic compounds significantly increase the rate of Ni transport under advective conditions and show measurable diffusive transport through intact monoliths of the cementitious backfill material.

Solubility constraints affecting the migration of selenium through the cementitious backfill of a geological disposal facility.

This work presents the study of the solubility of selenium under cementitious conditions and its diffusion, as SeO3(2-), through monolithic cement samples. The solubility studies were carried out under alkaline conditions similar to those anticipated in the near-field of a cement-based repository for low- and intermediate-level radioactive waste. Experiments were conducted in NaOH solution, 95%-saturated Ca(OH)2, water equilibrated with a potential backfill material (Nirex reference vault backfill, NRVB) and in solutions containing cellulose degradation products, with and without reducing agents. The highest selenium concentrations were found in NaOH solution. In the calcium-containing solutions, analysis of the precipitates suggests that the solubility controlling phase is Ca2SeO3(OH)2·2H2O, which appears as euhedral rhombic crystals. The presence of cellulose degradation products caused an increase in selenium concentration, possibly due to competitive complexation, thereby, limiting the amount of calcium available for precipitation. Iron coupons had a minor effect on selenium solubility in contrast to Na2S2O4, suggesting that effective reduction of Se(IV) occurs only at Eh values below -300mV. Radial through-diffusion experiments on NRVB and in a fly ash cement showed no evidence of selenium breakthrough after one year. However, autoradiography of the exposed surfaces indicated that some migration had occurred and that selenium was more mobile in the higher porosity backfill than in the fly ash cement.

Effect of anthropogenic organic complexants on the solubility of Ni, Th, U(IV) and U(VI).

The influence of anthropogenic organic complexants (citrate, EDTA and DTPA from 0.005 to 0.1M) on the solubility of nickel(II), thorium(IV) and uranium (U(IV) and U(VI)) has been studied. Experiments were carried out in 95%-saturated Ca(OH)2 solutions, representing the high pH conditions anticipated in the near field of a cementitious intermediate level radioactive waste repository. Results showed that Ni(II) solubility increased by 2-4 orders of magnitude in the presence of EDTA and DTPA and from 3 to 4 orders of magnitude in the case of citrate. Citrate had the greatest effect on the solubility of Th(IV) and U(IV)/(VI). XRD and SEM analyses indicate that the precipitates are largely amorphous; only in the case of Ni(II), is there some evidence of incipient crystallinity, in the form of Ni(OH)2 (theophrastite). A study of the effect of calcium suggests that U(VI) and Ni(II) may form metal-citrate-OH complexes stabilised by Ca(2+). Thermodynamic modelling underestimates the concentrations in solution in the presence of the ligands for all the elements considered here. Further investigation of the behaviour of organic ligands under hyperalkaline conditions is important because of the use of the thermodynamic constants in preparing the safety case for the geological disposal of radioactive wastes.

Variation patterns of nitric oxide in Catalonia during the period from 2001 to 2006 using multivariate data analysis methods.

Multivariate data analysis methods are applied to study of the geographical and temporal distribution of nitric oxide (NO) in Catalonia (North-East Spain), measured during the period 2001-2006 in 50 sampling stations. Principal component analysis (PCA) and Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) were applied for that purpose. The simultaneous analysis of NO data from sampling stations showed that its geographical distribution was rather uniform during the period considered. When three individual sampling stations were considered (two urban sites and one rural location), three different temporal patterns were resolved, with marked daily-night changes mainly attributed to traffic and also, important winter-summer seasonal variations. A decreasing trend in the levels of NO has been also observed in recent years. Comparison with nitrogen dioxide (NO(2)) profiles shows that the daily variation is quite similar to the NO variation, however NO(2) displays very little oscillations along the seasons and no reduction of its concentration was observed in the last years, contrasting with NO tendencies. The use of MCR-ALS is confirmed to be a useful method to improve interpretability in atmospheric contamination studies. The use of non-negativity and trilinearity constraints is shown to provide improved interpretations of the different contamination patterns in environmental terms.

Assessment of the environmental and physiological processes determining the accumulation of organochlorine compounds in European mountain lake fish through multivariate analysis (PCA and PLS).

The presence of organochlorine compounds (OCs)-namely hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorobiphenyls (PCBs #28, 52, 101, 118, 138, 153 and 180), dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethane (DDE)-was examined in various fish tissues (muscle and liver) sampled in 23 mountain lakes in Europe. The dependence of these organochlorine compounds on geographical parameters (altitude, longitude, latitude and temperature) and physiological parameters (lipid content, age, weight and size) was assessed. Principal components analysis (PCA) and partial least squares (PLS) models were used for the analyses. PCA results showed that organochlorine compound concentrations in fish tissues increased with increasing altitude and decreasing temperatures. This trend appeared to be more marked for the less volatile compounds. Some differences were found between the muscle and liver in the effects of the percentage of lipids on the accumulation of organochlorine compounds and the behaviour of HCB. Moreover, PCBs tended to accumulate more in liver rather than in muscle. PCA scores clearly differentiated samples according to the lake of origin. PLS models confirmed that temperature and altitude were the main factors influencing the accumulation of most organochlorine compounds in the lipids of the fish tissue.

Temporal characterisation of river waters in urban and semi-urban areas using physico-chemical parameters and chemometric methods.

Three sampling campaigns were carried out in rivers located at two hydrographic basins affected by urban and semi-urban areas around the Metropolitan area of A Coruña (ca. 500,000 inhabitants, NW-Spain) to study local and temporal variations of 21 physicochemical parameters (pH, conductivity, Cl-, SO4(2-), SiO2, Ca2+, Mg2+, Na+, K+, hardness, NO3(-), NO2(-), NH4(+), COD, PO4(3-), Zn2+, Cu2+, Mn2+, Pb2+, alkalinity and acidity) in 23 sampling points. The temporal evolution of the water quality was assessed by matrix augmentation principal components analysis (MA-PCA) and parallel factor analysis (PARAFAC). Moreover, classical principal components analysis (PCA) (one per sampling campaign) was applied with exploratory and comparison purposes. The first factor of the different studies comprised variables associated to the mineral content and it differentiated the samples according to their hydrographic basins. The second factor was mainly associated to organic matter, from domestic wastes and decomposition of natural debris. The temporal evolution of the water quality was mostly related to seasonal increments of the physicochemical parameters defining the decomposition of the organic matter. The three models applied (PCA, MA-PCA and PARAFAC) led to similar conclusions, nonetheless, MA-PCA excelled, since the refolding of scores provided more straightforward and convenient overview of sample time and geographical variations than individual PCA and it is more flexible and adaptable to environmental studies than PARAFAC.

Handling complex effects in slurry-sampling-electrothermal atomic absorption spectrometry by multivariate calibration.

Analysis of solid samples by slurry-sampling-electrothermal atomic absorption spectrometry (SS-ETAAS) can imply spectral and chemical interferences caused by the large amount of concomitants introduced into the graphite furnace. Sometimes they cannot be solved using stabilized temperature platform furnace (STPF) conditions or typical approaches (previous sample ashing, use of chemical modifiers, etc.), which are time consuming and quite expensive. A new approach to handle interferences using multivariate calibrations (partial least squares, PLS, and artificial neural networks, ANN) is presented and exemplified with a real problem consisting on determining Sb in several solid matrices (soils, sediments and coal fly ash) as slurries by ETAAS. Experimental designs were implemented at different levels of Sb to develop the calibration matrix and assess which concomitants (seven ions were considered) modified the atomic signal mostly. They were Na+ and Ca2+ and they induced simultaneous displacement, depletion (enhancement) and broadening of the atomic peak. Here it is shown that these complex effects can be handled in a reliable, fast and cost-effective way to predict the concentration of Sb in slurry samples of several solid matrices. The method was validated predicting the concentrations of five certified reference materials (CRMs) and studying its robustness to current ETAAS problems. It is also shown that linear PLS can handle eventual non-linearities and that its results are comparable to more complex (non-linear) models, as those from ANNs.

Microwave-assisted extraction and ultrasonic slurry sampling procedures for cobalt determination in geological samples by electrothermal atomic absorption spectroscopy.

Slurry sampling is compared to microwave-assisted acid digestion for cobalt determination in soil/sediment samples by electrothermal atomic absorption spectrometry (ETAAS). Furnace temperature programs and appropriate amounts of three chemical modifiers were optimised in order to get the highest signals and good separations between the atomic and background signals. Using nitric acid (0.5% (v/v)) as liquid medium, no chemical modifier was needed. The detection limit, based on integrated absorbance, was 0.04mugg(-1) for digests and slurries. Within-batch precision and analytical recoveries were satisfactory for both procedures. Accuracy was tested by analysing a reference soil and a sediment from IRMM. The methods were further compared employing a set of roadside soils and estuarine sediments. As no significant differences (95% confidence) were found, practical analytical properties were suggested in order to select one of them.

Slurry sampling for direct analysis of solid materials by electrothermal atomic absorption spectrometry (ETAAS). A literature review from 1990 to 2000.

The determination of trace metals in solid samples has traditionally been performed by acid digestion and subsequent measurement by a suitable instrumental technique. This dissolution step is time-consuming and it shows important drawbacks. For these reasons, in the past years many efforts have been focused on the direct analysis of solid samples. Among the developed methodologies, slurry sampling-electrothermal atomic absorption spectrometry combines the significant advantages of the solid and liquid sampling methods, and it can be already considered as a mature technique, that is widely utilized for metal determination in both organic and inorganic matrices, even for routine analysis. Accordingly, this work gives a retrospective view of the progresses of this technique during the past decade (1990-2000).

Chemical modifiers for direct determination of cobalt in coal combustion residues by ultrasonic slurry-sampling-ETAAS.

Five modifiers were tested for the direct determination of cobalt in coal fly ash and slag by ultrasonic slurry-sampling electrothermal atomic absorption spectrometry (USS-ETAAS). The furnace temperature programs and the appropriate amount for each modifier were optimized to get the highest signal and the best separation between the atomic and background signals. Nitric acid (0.5% v/v) was the most adequate chemical modifier for cobalt determination, selecting 1,450 degrees C and 2,100 degrees C as pyrolysis and atomization temperatures, respectively. This modifier also acts as liquid medium for the slurry simplifying the procedure. The remaining modifiers enhanced the background signal, totally overlapped with cobalt peak. The method optimized gave a limit of detection of 0.36 microg g(-1), a characteristic mass of 13 +/- 1 pg and an overall-method precision which is highly satisfactory (<7%, RSD). The method was validated by analyzing two certified coal fly ash materials, and satisfactory recoveries were obtained (83-90%) and no statistical differences were observed between the experimental and the certified cobalt concentrations. Additionally, certified sediment, soil and urban particulate matter were assayed; again good results were obtained. The developed methodology was used to determine cobalt in several coal combustion residues from five Spanish power plants.