In Southern Spain, as in other semi-arid zones, plants used for the phytoremediation of heavy metal-contaminated sites must be able to withstand not only the challenging soil conditions but also seasonal drought and high temperatures. A pot assay was carried out to determine the ability of soil amendments to promote the survival and growth of the seedlings of two native species, Atriplex halimus L. (Amaranthaceae) and Bituminaria bituminosa (L.) C.H. Stirton (Fabaceae), in two heavy metal-contaminated soils, one of which also had a high level of arsenic (As). Restriction of A. halimus shoot growth in the non-amended soils appeared to be due to deficiency of nitrogen, phosphorus (P) and potassium (K) and in the more highly contaminated soil to lead (Pb) toxicity. Shoot biomass of A. halimus in the more highly contaminated soil was increased significantly by compost addition, due to increased uptake of K and P and decreased tissue Pb. The lack of effect of compost on B. bituminosa growth in this soil, despite a large increase in tissue K, may have been due to elevated tissue levels of As and Pb and the high soil salinity. The combination of A. halimus and compost addition seems appropriate for the phytostabilisation of contaminated semi-arid sites.

The aim of the study was to determine whether the application of superphosphate fertiliser to soils contaminated with mine wastes can inhibit metal and metalloid mobility (Cu, Pb, Zn, Cd, Fe, Mn, As, Sb) in the long term. Contaminated soils contained sulfide- and sulfate-rich waste materials from the Broken Hill and Mt Isa mining centres. Results of long-term (10 months) column experiments demonstrate that fertiliser amendment had highly variable effects on the degree of metal and metalloid mobilisation and capture. Rapid release of metals from a sulfate-rich soil showed that phosphate amendment was ineffective in stabilising highly soluble metal-bearing phases. In a sulfide-rich soil with abundant organic matter, complexing of metals with soluble organic acids led to pronounced metal (mainly Cd, Cu and Zn) release from fertiliser-amended soils. The abundance of pyrite, as well as the addition of fertiliser, caused persistent acid production over time, which prevented the formation of insoluble metal phosphate phases and instead fostered an increased mobility of both metals and metalloids (As, Cd, Cu, Sb, Zn). By contrast, fertiliser application to a sulfide-rich soil with low organic carbon content and a sufficient acid buffering capacity to maintain near-neutral pH resulted in the immobilisation of Pb in the form of newly precipitated Pb phosphate phases. Thus, phosphate stabilisation was ineffective in suppressing metal and metalloid mobility from soils that were rich in organic matter, contained abundant pyrite and had a low acid buffering capacity. Phosphate stabilisation appears to be more effective for the in situ treatment of sulfide-rich soils that are distinctly enriched in Pb and contain insignificant concentrations of organic matter and other metals and metalloids.

The adsorption of As(III), As(V), Se(IV) and Se(VI) by seawater neutralized red mud and alum water treatment sludge was investigated and compared using the batch adsorption technique. For water treatment sludge, adsorption of As(V), Se(IV) and Se(VI), at equimolar concentrations of added metalloid, declined with increasing pH. The decline was rapid above pH 4.0 for Se(VI), above pH 5.0 for Se(IV) and above pH 6.0 for As(V). Adsorption of As(III) increased with increasing pH up to pH 9.0 and then declined. For red mud, adsorption of As(V), Se(IV) and Se(VI) showed a maximum at about pH 5.0 and for As(III) adsorption remained relatively constant over the pH range 2.0–10.0 after which it declined. Water treatment sludge removed 50 % or more of solution As(V) between pH 2.0 and 10.8, Se(IV) between 2.0 and 8.9, Se(VI) between 2.0 and 5.8 and As(III) between 8.4 and 10.9. By contrast, red mud showed less than 25 % adsorption of added Se(VI) and As(III) over the entire pH range tested (2.0–12.0) and reached 50 % or more for As(V) only over the pH range 4.0–6.9 and for Se(IV) between pH 4.3 and 5.6. At pH 5.0, adsorption of As(III) and Se(IV) was better described by the Langmuir than Freundlich equation but the reverse was the case for As(V) and Se(VI). Kinetic data for adsorption of all four oxyanions onto both adsorbents correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. NaOH was more effective at removing adsorbed metals from both adsorbents than HNO₃. Water treatment sludge maintained its As(III) and Se(IV) adsorption capability at greater than 70 % of that added over eight successive cycles of adsorption/regeneration using 0.5 M NaOH as a regenerating agent. By contrast, for red mud, As(V) adsorption capacity declined very rapidly after three adsorption/desorption cycles and that for Se(IV) it decreased progressively with increasing numbers of cycles. It was concluded that water treatment sludge is a suitable material to develop as a low-cost adsorbent for removal of heavy metal oxyanions from wastewater streams.

Red lead (Pb3O4) has been used extensively in the past as an anti-corrosion paint for the protection of steel constructions. Prominent examples being some of the 200,000 high-voltage pylons in Germany which have been treated with red lead anti-corrosion paints until about 1970. Through weathering and maintenance work, paint compounds and particles are deposited on the soils beneath these constructions. In the present study, six such “pylon soils” were investigated in order to characterize the plant availability and plant uptake of Pb, Cd, and Zn. For comparison, three urban soils with similar levels of heavy metal contamination were included. One phase extractions with 1 M NH4NO3, sequential extractions (seven steps), and extractions at different soil pH were used to evaluate the heavy metal binding forms in the soil and availability to plants. Greenhouse experiments were conducted to determine heavy metal uptake by Lolium multiflorum and Lactuca sativa var. crispa in untreated and limed red lead paint contaminated soils. Concentrations of Pb and Zn in the pylon soils were elevated with maximum values of 783 mg Pb kg−1 and 635 Zn mg kg−1 while the soil Cd content was similar to nearby reference soils. The pylon soils were characterized by exceptionally high proportions of NH4NO3-extractable Pb reaching up to 17% of total Pb. Even if the relatively low pH of the soils is considered (pH 4.3–4.9), this appears to be a specific feature of the red lead contamination since similarly contaminated urban soils have to be acidified to pH 2.5 to achieve a similarly high Pb extractability. The Pb content in L. multiflorum shoots reached maximum values of 73 mg kg−1 after a cultivation time of 4 weeks in pylon soil. Lime amendment reduced the plant uptake of Pb and Zn significantly by up to 91%. But L. sativa var. crispa cultivated on soils limed to neutral pH still contained critical Pb concentrations (up to 0.6 mg kg−1 fresh weight). Possible mechanisms for the exceptionally high plant availability of soil Pb derived from red lead paint are discussed.

A set of indices was developed in order to classify the vulnerability of agricultural land to water and nitrogen losses (LOS), setting a basis for the integrated water resources management in agricultural systems. To calibrate the indices using multiple regression analysis, the simulation results of Groundwater Loading Effects of Agricultural Management Systems (GLEAMS) model for combinations of different soil properties, topography, and climatic conditions of a reference field crop were used as “observed values.” GLEAMS quantified (1) the annual losses of the percolated water beneath the root zone, (2) the annual losses of the surface runoff, (3) the annual losses of the nitrogen leaching beneath the root zone, and (4) the annual losses of nitrogen through the surface runoff, which were used to calibrate the following indices LOSW-P, LOSW-R, LOSN-PN, and LOSN-RN, respectively. All the simulations to gain the LOS indices were carried out for the same reference field crop, the same nitrogen fertilization, and the same irrigation practice, in order to obtain the intrinsic vulnerability of agricultural land to water and nitrogen losses. The LOS indices were also combined to derive nitrogen concentrations in the percolated and in the runoff water. Finally, the connection of LOS indices with the groundwater was performed using an additional equation, which determines the minimum transit time of the percolated water to reach the groundwater table.

This paper examined the ability of honeycomb biomass (HC), a by-product of the honey industry, to remove Pb(II), Cd(II), Cu(II), and Ni(II) ions from aqueous solutions. The equilibrium adsorptive quantity was determined as a function of the solution pH, amount of biomass, contact time, and initial metal ion concentration in a batch biosorption technique. Biosorbent was characterized by Fourier transform infrared (FTIR), scanning electron microscopy with energy-dispersive X-ray, and X-ray diffraction studies. FTIR spectral analysis confirmed the coordination of metals with hydroxyl, carbonyl, and carboxyl functional groups present in the HC. The metals uptake by HC was rapid, and the equilibrium time was 40 min at constant temperature and pH. Sorption kinetics followed a nonlinear pseudo-second-order model. Isotherm experimental data were fitted to Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models in nonlinear forms. The mechanism of metal sorption by HC gave good fits for Langmuir model, and the affinity order of the biosorbent for four heavy metals was Pb(II)>Cd(II)>Cu(II)>Ni(II). The thermodynamic studies for the present biosorption process were performed by determining the values of ΔG°, ΔH°, and ΔS°, and it was observed that biosorption process is endothermic and spontaneous. This work provides an efficient and easily available environmental friendly honeycomb biomass as an attractive option for removing heavy metal ions from water and wastewater.

This study investigated the formation of volatile carbonaceous disinfection by-products (DBPs) and nitrogenous DBPs from chlorination of oxytetracycline. Six DBPs were identified including chloroform (CF), 1,1-dichloroacetone, 1,1,1-trichloroacetone (TCP), dichloroacetonitrile (DCAN), trichloroacetonitrile, and trichloronitromethane. DBP yields varied with different reaction conditions, including chlorine concentration, reacting time, pH, and bromide concentration. The highest DBP yields were found at Cl₂/C mass ratio and reaction time of 5 and 3 days, respectively. The solution pH had significant influence on CF, DCAN, and 1,1,1-TCP formation. The concentration of CF increased with the increase of pH, while DCAN and 1,1,1-TCP yields were high at acidic pH and decreased greatly under alkaline conditions. In the presence of bromide, the DBP composition shifted to multiple bromide compounds, including bromodichloromethane, dibromochloromethane, bromoform, bromochloroacetonitrile, and dibromoacetonitrile.

In this study, the applications of mesoporous materials based on silica, and those with modifications, namely post-synthetic grafting, co-condensation, and pure SBA-15, were investigated for the removal of phosphate from sewage. The mesostructures were confirmed by X-ray diffraction, Brunauer–Emmett–Teller, Fourier transform infrared spectroscopy, and transmission electron microscopy. The absorption of phosphate by the mesoporous adsorbents was examined, using different adsorption models to describe the equilibrium and kinetic data. The maximum adsorption capacities of the mesostructured adsorbents were found to be 69.970, 59.890, and 2.018 mg/g for the co-condensation, post-synthetic grafting, and pure SBA-15, respectively. The kinetic data showed that the adsorption of phosphate onto three different mesostructures followed the pseudo-first-order kinetic model.

This study examined the impact of oxidative stress indicated by thiobarbituric acid reactive substances (TBARS) and protein carbonyl (PC), induced by intensive exercise and cadmium chloride (CdCl₂) on ethoxyresorufin-O-deethylase (EROD) activity in juvenile carp (Cyprinus carpio). In the first experiment, fish were divided into three groups: (1) control, (2) carp exposed to intensive exercise, and (3) carp that was not exercised but previously, as well as carp in group 2, received single dose of 3-methylcholantrene (3-MC). The third and sixth day fish were sacrificed and the measurements were conducted. In the second experiment, fish were divided into (1) control, (2) carp in water containing CdCl₂, and (3) carp in dechlorinated tap water (2 and 3 received single dose of 3-MC on the seventh day after exposure to CdCl₂). The carp were killed 6 days later and livers were excised for biochemical analyses. In the first experiment, on the sixth day after treatment with 3-MC, results show statistically significant increase in EROD activity in non-exercised carp, while that increase in carp exposed to intensive exercise was significantly lower. Three days after exposure to 3-MC, statistically significant increase in TBARS was observed in both exercised and non-exercised carp. Six days after exposure to 3-MC, PC levels were significantly higher in exercised carp. Pretreatment with CdCl₂, in the second experiment, caused oxidative stress and reduction of EROD activity. Results show linkage between expression of EROD activity and oxidative stress biomarkers and possible influence of oxidative stress on the cell membrane structures and consequently on EROD activity.

This paper presents a comprehensive study on the quality of surface and groundwater in an environmentally sensitive karstic watershed strongly pressed by urban growth. The objective of the study was to assess the integrated effects of human activities and natural characteristics of karstic environments on the quality of surface and groundwater using multivariate statistical techniques. Data from 18 physical, chemical, and microbiological water quality variables obtained throughout a hydrological year were analyzed using principal components analysis (PCA) and cluster analysis. The PCA was carried out individually for surface water and groundwater. Our goal was to study the behavior of the water quality variables at each of these systems, as well as to infer the importance of these variables on the dynamics of the water resources in the region. Our results for surface water showed that the 18 original variables could be reduced to five principal components which together accounted for 69% of the total variation in the data, whereas for groundwater, 70% of the total variation in the data was explained by five principal components. In order to evaluate the impacts of anthropic activities on the water quality at the monitoring locations, the cluster analysis was applied to the ten sampling points. The analysis identified five clusters, two of which are formed by points with low contamination levels and three where the anthropic interference is noticeable. The results suggest the existence of specific contamination sources in many points, including in the groundwater, and highlight the natural vulnerability of the karstic environments.