Malachite green (MG), a recalcitrant, carcinogenic, and mutagenic triphenylmethane dye, was decolorized and detoxified using crude manganese peroxidase (MnP) prepared from the white rot fungus Irpex lacteus F17. In this study, the key factors (pH, temperature, MG, Mn²⁺, H₂O₂, MnP) in these processes were investigated. Under optimal conditions, 96 % of 200 mg L⁻¹ of MG was decolorized when 66.32 U L⁻¹ of MnP was added for 1 h. The K ₘ, V ₘₐₓ, and k cₐₜ values were 109.9 μmol L⁻¹, 152.8 μmol L⁻¹ min⁻¹, and 44.5 s⁻¹, respectively. The decolorization of MG by MnP followed first-order reaction kinetics with a kinetic rate constant of 0.0129 h⁻¹. UV–vis and UPLC analysis revealed degradation of MG. Furthermore, seven different intermediates formed during the MnP treatment of 0.5 h were identified by LC-TOF-MS. These degradation products were generated via two different routes by either N-demethylation of MG or the oxidative cleavage of the C–C double bond in MG. Based on ecotoxicity analyses performed on bacteria and algae, it was confirmed that MG metabolites produced by the MnP-catalyzed system were appreciably less toxic than the parent compound. These studies indicate the potential use of this enzyme system in the clean-up of aquatic and terrestrial environments.

The need to increase water productivity in agriculture has been stressed as one of the most important factors to achieve greater agricultural productivity and sustainability. The main aim of this paper is to investigate whether there are differences in water use efficiency (WUE) between farmers who participate in water markets and farmers who do not participate in them. Moreover, the use of a non-radial data envelopment analysis model allows to compute global efficiency (GE), WUE as well the efficiency in the use of other inputs such as fertilizers, pesticides, energy, and labor. In a second stage, external factors that may affect GE and WUE are explored. The empirical application focuses on a sample of farmers located in Limarí Valley (Chile) where regulated permanent water rights (WR) markets for surface water have a long tradition. Results illustrate that WR sellers are the most efficient in the use of water while non-traders are the farmers that present the lowest WUE. From a policy perspective, significant conclusions are drawn from the assessment of agricultural water productivity in the framework of water markets.

Monitoring the levels of trace elements in hair can allow estimating the effects of the geographical location and also can provide a notion of the metal body burden. However, the use of human hair is controversial due to the different confounding factors that could affect the presence of trace elements in hair. As a result, a comprehensive monitoring study was performed in Alcalá de Henares, one of the major cities in the Madrid region, Spain. Trace elements have been monitored in urban topsoils and in human hair of two well-defined and healthy groups of population: children (6–9 years) and adolescents (13–16 years). The city was divided into four areas or zones with different characteristics to assess the possible effect of area of residence and age in the presence of Al, As, Be, Cd, Cr, Cu, Hg, Mn, Pb, Sn, Ti, Tl and Zn in soils and hair. There is no current hypothesis that explains the possible effect of the area of monitoring in the distribution of Be, Cr, Ni, Sn and Ti found in these urban soils, maybe because urban soils receive high disturbance, and there are many factors involved. The presence of most of the trace elements monitored was significantly higher in the hair of the children population, except for Sn and Zn. This could be attributed mainly to dietary habits. Other factors influencing metal content in hair such as environmental factors would have had a minimal effect in the population groups here studied. Finally, none of the levels of trace elements studied in hair were significantly correlated with levels measured in the topsoils of public parks in Alcalá de Henares, with the exception of Pb in adolescent participants.

The Mar Piccolo of Taranto (Ionian Sea, Southern Italy) is a semi-enclosed and strongly polluted basin. For decades, it has been subjected to different anthropogenic impacts. These stressors caused severe sediments contamination with high concentration of different pollutants (PAHs, PCB, heavy metals). In order to assess the current status of sediments contamination, an ecotoxicological investigation combined with chemical analysis (heavy metals, PAH, and PCB) has been performed. In order to derive ecologically relevant conclusions, a multiorganisms and multiend-points approach has been applied, exposing organisms from different trophic levels to elutriate and whole sediment. The battery of bioassays consists of a microalgal growth inhibition test (Dunaliella tertiolecta), acute and sublethal assays (end-points: mortality, immobilization and swimming speed alteration) on crustaceans larvae and juveniles, and rotifers (Amphibalanus amphitrite, Artemia salina, Corophium insidiosum and Brachionus plicatilis), and embryotoxicity test on echinoderms (Paracentrotus lividus). Considering the high levels of sediment contamination highlighted from chemical analysis, an unexpected very low toxic effect was observed, even considering the sublethal end-point (larval swimming speed alteration). The results of this study suggest a very complex contaminants dynamic in the Mar Piccolo sediments that, despite a strong level of contamination, seems to not affect in a proportional manner the biological compartment.

The effects of sediment resuspension on the fate of metals and polychlorinated biphenyls (PCBs) were studied by using a short-term small reactor. Sediments and water were collected nearby the most contaminated site of the Mar Piccolo of Taranto. Contaminant partitioning was calculated between the solid and water phases and, in the latter, between the dissolved and particulate phases and related to physical–chemical variables. Before and after resuspension, metal concentrations in sediments did not vary remarkably. Except for Cd, all the analyzed metals exceeded by many folds both threshold effect level (TEL) and probable effect level (PEL) SQGs. Igeo index values for Hg designated the sediment quality as extremely polluted for Pb, Cu and moderately polluted for Zn. In the dissolved phase, Mn increased of about 70 times, Fe of about 7 times and Hg and Zn of 4 and 3 times, respectively. PCBs in sediments before and after resuspension did not vary for more than 15 %. PCB concentrations exceeded for more than ten times PEL values. After resuspension, PCBs increased from 0.82 to 4.82 ng L⁻¹ in the dissolved phase and from 0.22 to 202.21 ng L⁻¹ in the particulate one. The dissolved phase was initially enriched in light- to mid-weight compounds. After resuspension, the particulate phase was enriched in heavier congeners. In particular, hexachlorobiphenyl-153, 149 and 138 together with heptachlorobiphenyl-180 and 187 accounted for 57 % of total PCBs. The dissolved organic carbon (DOC) that increased from 1.31 to 8.55 mg L⁻¹ likely influenced the fate of metals and PCBs in the dissolved and particulate phases. Despite that the residence time of the contaminated resuspended sediments in the water column is limited, they are still highly toxic for the pelagic trophic web.

Sediments function both as a sink and a source of pollutants in aquatic ecosystems and may impose serious effects on benthic organisms and human health. As one of the largest estuaries in the world, the Yangtze River estuary suffers from abundant wastewater from the coastal cities. In this study, the zebrafish (Danio rerio) embryos were employed in the fish embryo test and a comet assay to evaluate the embryotoxicity and genotoxicity of the sediments from the Yangtze River estuary, respectively. Results showed that the sediments from the Yangtze River estuary significantly increased mortality, induced development abnormalities, and reduced hatching rate and heart rate of zebrafish embryos after 96 h of exposure. Significant genotoxicity was observed in the samples relative to the controls. Relatively low-level embryotoxicity and genotoxicity of sediments were found in the Yangtze River compared with other river systems. Toxic responses were also discussed in relation to the analyzed organic contaminants in sediments. More attention should be paid to non-priority pollutant monitoring in the Yangtze River estuary.

The quality of the indoor air can provide very useful information for the artwork conservation. The aim of the study was to evaluate the microbial concentration inside six document repositories of the National Archive of the Republic of Cuba in two months of 1 year. The repositories are large, high, and have a natural cross-ventilation system. The microbial sampling was done in July 2010 (summer or rainy month) and February 2011 (winter or dry month) using the SAS Super 100 biocollector at 100 L/min. An appropriate selective culture media were used to isolate fungi and bacteria. A high total microbial concentration on the north side of the building in two studied months was observed. The fungal concentrations were significantly higher in July 2010 in all repositories, while the bacterial concentrations were significantly higher mostly in February 2011 only in repositories located on the first and second floor of the building. Eight fungal genera in the indoor air of all environments were isolated. Regardless of the side of the analyzed building, Penicillium, Aspergillus, and Cladosporium were the predominant genera. Aspergillus flavus and Aspergillus niger were the species isolated in almost all of the analyzed repositories in the studied months. Gram-positive bacteria prevailed among bacterial groups isolated from indoor air repositories, and some percentages corresponded to the genera Bacillus and Streptomyces. In Cuba, the temperature and relative humidity are high during the whole year but the natural ventilation plays an important role in retarding microbial growth on materials.

A comparative evaluation of paperboard mill sludge (PMS) versus mixed culture bacteria (MCB) as inoculum for hydrogen production from paperboard mill wastewater (PMW) was investigated. The experiments were conducted at different initial cultivation pHs, inoculums to substrate ratios (ISRs gVS/gCOD), and hydraulic retention times (HRTs). The peak hydrogen yield (HY) of 5.29 ± 0.16 and 1.22 ± 0.11 mmol/gCODᵢₙᵢₜᵢₐₗ was occurred at pH = 5 for MCB and PMS, respectively. At pH of 5, the HY and COD removal achieved the highest values of 2.26 ± 0.14 mmol/gCODᵢₙᵢₜᵢₐₗ and 86 ± 1.6 % at ISR = 6 for MCB, and 2.38 ± 0.25 mmol/gCODᵢₙᵢₜᵢₐₗ and 60.4 ± 2.5 % at ISRs = 3 for PMS. The maximum hydrogen production rate was 93.75 ± 8.9 mmol/day at HRT = 9.6 h from continuous upflow anaerobic reactor inoculated with MCB. Meanwhile, the 16S ribosomal RNA (rRNA) gene fragments indicated a dominance of a novel hydrogen-producing bacterium of Stenotrophomonas maltophilia for PMS microbial community. On the other hand, Escherichia fergusonii and Enterobacter hormaechei were the predominant species for MCB.

DDT and mercury (Hg) contamination in the Toce River (Northern Italy) was caused by a factory producing technical DDT and using a mercury-cell chlor-alkali plant. In this study, DDT and Hg contamination and bioavailability were assessed by using different approaches: (1) direct evaluation of sediment contamination, (2) assessment of bioaccumulation in native benthic invertebrates belonging to different taxonomic/functional groups, and (3) evaluation of the in situ bioavailability of DDT and Hg using passive samplers. Sampling sites were selected upstream and downstream the industrial plant along the river axis. Benthic invertebrates (Gammaridae, Heptageniidae, and Diptera) and sediments were collected in three seasons and analyzed for DDT and Hg content and the results were used to calculate the biota sediment accumulation factor (BSAF). Polyethylene passive samplers (PEs) for DDT and diffusive gradients in thin films (DGTs) for Hg were deployed in sediments to estimate the concentration of the toxicants in pore water. Analysis for (DDx) were performed using GC-MS. Accuracy was within ±30 % of the certified values and precision was >20 % relative standard deviation (RSD). Total mercury concentrations were determined using an automated Hg mercury analyzer. Precision was >5 % and accuracy was within ±10 % of certified values. The results of all the approaches (analysis of sediment, biota, and passive samplers) showed an increasing contamination from upstream to downstream sites. BSAF values revealed the bioavailability of both contaminants in the study sites, with values up to 49 for DDx and up to 3.1 for Hg. No correlation was found between values in sediments and the organisms. Concentrations calculated using passive samplers were correlated with values in benthic invertebrates, while no correlation was found with concentrations in sediments. Thus, direct analysis of toxicant in sediments does not provide a measurement of bioavailability. On the contrary, analysis of bioaccumulation in benthic organisms provides the most realistic picture of the site-specific bioavailability of DDx and Hg, but this approach is time-consuming and not always feasible. On the other hand, the in situ deployment of passive samplers proved to be a powerful tool, providing a good surrogate measure of bioaccumulation.

Surface sediment from large and eutrophic Lake Chaohu was investigated to determine the occurrence, spatial distribution, sources, and risks of polychlorinated biphenyls (PCBs) and heavy metals in one of the five biggest freshwater lakes in China. Total concentration of PCBs (Σ₃₄PCBs) in Lake Chaohu was 672 pg g⁻¹ dry weight (dw), with a range of 7 to 3999 pg g⁻¹ dw, which was lower than other water bodies worldwide. The majority of heavy metals were detected at all sampling locations, except for Sr, B, and In. Concentrations of Al, Fe, Ca, Mn, Sr, Co, Zn, Cd, Pb, and Hg were similar to that reported for other lakes globally. Concentrations of K, Mg, Na, Li, Ga, and Ag were greater than the average, whereas those of Cr, Ni, and Cu were lower. Cluster analysis (CA) and positive matrix factorization (PMF) yielded accordant results for the source apportionment of PCBs. The technical PCBs and microbial degradation accounted for 34.2 % and 65.8 % of total PCBs using PMF, and PMF revealed that natural and anthropogenic sources of heavy metals accounted for 38.1 % and 61.8 %, respectively. CA indicated that some toxic heavy metals (e.g., Cd, In, Tl, and Hg) were associated with Ca–Na–Mg minerals rather than Fe–Mn minerals. The uncorrelated results between organic matter revealed by pyrolysis technology and heavy metals might be caused by the existence of competitive adsorption between organic matter and minerals. PCBs and heavy metals were coupling discharge without organochlorine pesticides (OCPs), but with polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs). No sediment sample exceeded the toxic threshold for dioxin-like PCBs (dl-PCBs) set at 20 pg toxicity equivalency quantity (TEQ) g⁻¹, (max dl-PCBs, 10.9 pg TEQ g⁻¹). However, concentrations of Ag, Cd, and Hg were at levels of environmental concern. The sediment in the drinking water source area (DWSA) was threatened by heavy metals from other areas, and some fundamental solutions were proposed to protect the DWSA.