Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

β-Estradiol and ethinyl-estradiol contamination in the rivers of the Carpathian Basin

17β-Estradiol (E2) and 17α-ethinyl estradiol (EE2), which are environmental estrogens, have been determined with LC-MS in freshwater. Their sensitive analysis needs derivatization and therefore is very hard to achieve in multiresidue screening. We analyzed samples from all the large and some small rivers (River Danube, Drava, Mur, Sava, Tisza, and Zala) of the Carpathian Basin and from Lake Balaton. Freshwater was extracted on solid phase and derivatized using dansyl chloride. Separation was performed on a Kinetex XB-C18 column. Detection was achieved with a benchtop orbitrap mass spectrometer using targeted MS analysis for quantification. Limits of quantification were 0.05 ng/L (MS1) and 0.1 ng/L (MS/MS) for E2, and 0.001 ng/L (MS1) and 0.2 ng/L (MS/MS) for EE2. River samples contained n.d.–5.2 ng/L E2 and n.d.–0.68 ng/L EE2. Average levels of E2 and EE2 were 0.61 and 0.084 ng/L, respectively, in rivers, water courses, and Lake Balaton together, but not counting city canal water. EE2 was less abundant, but it was still present in almost all of the samples. In beach water samples from Lake Balaton, we measured 0.076–0.233 E2 and n.d.–0.133 EE2. A relative high amount of EE2 was found in river Zala (0.68 ng/L) and in Hévíz-Páhoki canal (0.52 ng/L), which are both in the catchment area of Lake Balaton (Hungary).     

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain)

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.     

Mercury bioaccumulation and phytotoxicity in two wild plant species of Almadén area

Mercury is a widely distributed environmental pollutant, able to induce toxicity in living organisms, including higher plants. Some plant species are able to grow in mine sites, like the Almadén zone in Spain. Our study focus on two of these plant species, Rumex induratus and Marrubium vulgare and their responses to natural Hg exposure. Total Hg concentration in the soil below the plants could be classified as toxic, although the available fraction was low. Hg availability was higher for the M. vulgare than for the R. induratus plot. Hg concentrations in field plants of R. induratus and M. vulgare grown on these soils can be considered as phytotoxic, although no symptoms of Hg toxicity were observed in any of them. According to the BAF ([Hg]_tissue/[Hg]_avail), R. induratus showed a higher ability in Hg uptake and translocation to shoots, as well as higher concentrations of MDA and –SH:Hg ratios, so that this plant is more sensitive to Hg than M. vulgare. The resistance to Hg and the capability to extract Hg from the soil make both M. vulgare and R. induratus good candidates for Hg phytoremediation of contaminated soils.     

Selected trace metals in oysters (Crassostrea iridescens) and sediments from the discharge zone of the submarine sewage outfall in Mazatlán Bay (southeast Gulf of California): chemical fractions and bioaccumulation factors

Concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the soft tissue of Crassostrea iridescens and the associated surface sediments (bulk and bioavailable metal concentrations) from an area influenced by a sewage outfall in Mazatlán Bay (southeast Gulf of California), were determined by atomic absorption spectrophotometry. Significant spatial differences in metal concentrations in both the bulk and bioavailable forms in the sediments were identified. An enrichment of Cu, Ni, Pb and Zn in sites located on a south-north transect was detected indicating a dominant influence of the sewage outfall toward the north. C. iridescens accumulated more Zn, Cu, Ni, Fe, Cd; and less Mn, Cr and Pb than were bioavailable in the sediments, as measured using conventional extraction analysis. The degree of enrichment and the bioavailable metal concentrations in the sediments of the south portion of Mazatlán Bay is discussed. The potential ability of C. iridescens as a biomonitor of metallic pollutants is postulated.     

Quantitative–spatial assessment of soil contamination in S. Francisco de Assis due to mining activity of the Panasqueira mine (Portugal)

Through the years, mining and beneficiation processes produces large amounts of As-rich mine wastes laid up in huge tailings and open-air impoundments (Barroca Grande and Rio tailings) that are the main source of pollution in the surrounding area once they are exposed to the weathering conditions leading to the formation of AMD and consequently to the contamination of the surrounding environments, in particularly soils. In order to investigate the environmental contamination impact on S. Francisco de Assis (village located between the two major impoundments and tailings) agricultural soils, a geochemical survey was undertaken to assess toxic metals associations, related levels and their spatial distribution, and to identify the possible contamination sources. According to the calculated contamination factor, As and Zn have a very high contamination factor giving rise to 65.4 % of samples with a moderate to high pollution degree; 34.6 % have been classified as nil to very low pollution degree. The contamination factor spatial distribution put in evidence the fact that As, Cd, Cu, Pb, and Zn soils contents, downstream Barroca Grande tailing, are increased when compared with the local Bk soils. The mechanical dispersion, due to erosion, is the main contamination source. The chemical extraction demonstrates that the trace metals distribution and accumulation in S. Francisco de Assis soils is related to sulfides, but also to amorphous or poorly crystalline iron oxide phases. The partitioning study allowed understanding the local chemical elements mobility and precipitation processes, giving rise to the contamination dispersion model of the study area. The wind and hydrological factors are responsible for the chemical elements transport mechanisms, the water being the main transporter medium and soils as one of the possible retention media.     

Remobilization of metals from slag and polluted sediments (case study: the canal of the Deûle River, northern France)

The anthropogenic impact on the environment in the last century has proven to be very negative due to the fast development of industry. A typical example is the De?le River in northern France, one of the most polluted sites in this region. The concentrations of Pb, Cd, Zn and Cu in river sediments are 300, 800, 50 and 15 times higher, respectively, than the background values. The present study was undertaken to evaluate the capacity of already polluted sediments to capture metals released from industrial wastes (slag). As it were, in spite of the high metal pollution level, sediments have still shown the ability to adsorb metals released from slag under the conditions provided. Their efficiency in "cleaning up" some of the metals (e.g. Pb) seems to be additionally enhanced in anoxic conditions. This study provided some additional information on the importance of sediments as a pollutant sink.     

Microbial communities to mitigate contamination of PAHs in soil—possibilities and challenges: a review

Background, aim, and scope  

Although highly diverse and specialized prokaryotic and eukaryotic microbial communities in soil degrade polycyclic aromatic hydrocarbons (PAHs), most of these are removed slowly. This review will discuss the biotechnological possibilities to increase the microbial dissipation of PAHs from soil as well as the main biological and biotechnological challenges.     

Response of microcrustacean communities from the surface—groundwater interface to water contamination in urban river system of the Jarama basin (central Spain)

In order to evaluate the water quality at the surface/groundwater interface (hyporheic zone), the pattern of microcrustacean assemblages in response to environmental stress caused by urban industrial contamination was studied in the Jarama River basin (central Spain) during high water discharges (March and April 2011). The clustering of biological variables and the concentration of urban contaminants in hyporheic waters showed that pristine hyporheic waters have moderate species diversity (two to seven species) and dominance of k strategist stygobites, whereas excessively contaminated sites are devoid by crustaceans. An intermediate level of disturbance in hyporheic waters is associated with a peak of species taxonomic diversity (four to nine species) and proliferation of r strategist more tolerant species. Typical species found in hyporheic zone, e.g., Paracyclops imminutus (Copepoda, Cyclopoida), Cryptocandona vavrai (Ostracoda) and Herpetocypris chevreuxi (Ostracoda), were good indicators of high concentrations of Cr, Mn, Ni, Cd, Pb and VOCs; whereas the stygobites do not show any significant correlation. The effectiveness of hyporheic crustaceans as efficient bioindicators for assessing the current ecological status of river ecosystems is emphasised.     

Uptake of heavy metals and As by Brassica juncea grown in a contaminated soil in Aznalcóllar (Spain): the effect of soil amendments

Two crops of Brassica juncea (L.) Czern. were grown in a field experiment, at the site affected by the toxic spillage of acidic, metal-rich waste in Aznalcóllar (Seville, Spain), to study its metal accumulation and the feasibility of its use for metal phytoextraction. The effects of organic soil amendments (cow manure and mature compost) and lime on biomass production and plant survival were also assessed; plots without organic amendment and without lime were used as controls. Plots, with or without organic amendment, having pH < 5 were limed for the second crop. Soil acidification conditioned plant growth and metal accumulation. The addition of lime and the organic amendments achieved higher plant biomass production, although effects concerning metal bioavailability and accumulation were masked somewhat by pH variability with time and between and within plots. Tissue metal concentrations of B. juncea were elevated for Zn, Cu and Pb, especially in leaves of plants from plots with low pH values (maxima of 2029, 71 and 55 microg g(-1), respectively). The total uptake of heavy metals in the plants was relatively low, emphasising the problems faced when attempting to employ phytoextraction for clean-up of pluri-contaminated sites.     

Characterization of non-extractable ¹⁴C- and ¹³C-sulfadiazine residues in soil including simultaneous amendment of pig manure

Recently, we reported on soil fate of SDZ residues amended with pig manure treated with 1?C-labeled sulfadiazine 1?C-SDZ). The first objective of the present study was to determine whether this strategy can be substituted by application of 1?C-SDZ to soil. The second objective was to characterize non-extractable SDZ residues by fractionation, size exclusion chromatography (SEC) and solid state 13C-NMR. The fate of 1?C-SDZ was examined for 28 d, using two soils with and without amendment of pig manure. Mineralization of 1?C-SDZ was low; extractable residues decreased to 7-30%. Compared to the previous study, results were similar. 1?C-SDZ derived bound radioactivity was found in HCl-washings, fulvic, humic acids and humin. According to SEC, one bound 1?C portion (70%) co-eluted with fulvic acids (above 910 g mol?1); the other consisted of adsorbed/entrapped 1?C-SDZ. The 13C-SDZ study was performed for 30 d; humic acids were examined by 13C-NMR. A signal (100-150 ppm) was referred to 13C-SDZ. SEC and 13C-NMR demonstrated rapid integration of SDZ into humics.     

Roles of regional hydrodynamic and trophic contamination in cadmium bioaccumulation by Pacific oysters in the Marennes-Oléron Bay (France)

The Marennes-Oléron Bay, hosting the largest oyster production in France, is influenced by the historic polymetallic pollution of the Gironde Estuary. Despite management efforts and decreasing emissions in the Gironde watershed, cadmium levels in oysters from the bay are close to the consumption limit (5 μg g⁻¹ dw, EC). From mid April to mid July 2009, we investigated the role of tidal resuspension and regional hydrodynamics on Cd speciation (seawater, SPM, phytoplankton, sediment, microphytobenthos) and bioaccumulation in 18 month-old oysters (gills, digestive glands, rests of tissues) reared under natural conditions (i) at ∼60 cm above the sediment and (ii) on the sediment surface. Dissolved and particulate Cd concentrations in surface and bottom waters were similar and constant over tidal cycle suggesting the absence of Cd release during sediment resuspension. Temporal dissolved and particulate Cd concentrations were closely related to Gironde Estuary water discharges, showing increasing concentrations during flood situations and decreasing concentrations afterwards. Cd depletion in the water column was associated with increasing Cd in the [20-100 μm] plankton fraction, suggesting Cd bioaccumulation. After 3 months, enrichment factors of Cd in tissues of oysters exposed in the water column and directly on the sediment were respectively 3.0 and 2.2 in gills, 4.7 and 3.2 in digestive glands and 4.9 and 3.4 in remaining tissues. Increasing Cd bioaccumulation in gills, digestive glands and remaining tissues can be related to elevated dissolved Cd in the bay, suggesting gill contamination via the direct pathway and subsequent internal redistribution of Cd to other organs and tissues. Elevated Cd contents in oysters reared on tables could be attributed to different trophic Cd transfer (phytoplankton versus microphytobenthos) or to different oyster metabolisms between the rearing conditions as suggested by metallothionein concentrations.     

Mercury contamination in alligators (Melanosuchus niger) from Mamirauá Reservoir (Brazilian Amazon) and human health risk assessment

Mercury (Hg) concentrations in muscles of wild alligators (Melanosuchus niger) from the Mamirauá Reservoir (a reference area in the Brazilian Amazon) and the human health risks associated with its consumption were assessed. The mean Hg concentration in alligator muscles was 0.407?±?0.114 μg/g (N?=?61). Close to 5 % of the muscle samples showed Hg levels above the World Health Organization guideline for fish consumption (0.5 μg/g). A positive and significant relationship was observed between Hg concentrations in muscle and the age of the specimens. The dose-response approach suggests that close to 27.4 years is required for half of the exposed specimens to attain 0.5 μg/g. The hazard quotient (HQ) is a risk indicator which defines the ratio of exposure level and a toxicological reference dose. HQ resulted above the unity for all the specimens when the ingestion rate for riverine communities (200 g of muscle per day) is considered, indicating the existence of hazard. When the ingestion rate for market consumers (28.57 g/day) is considered, the risks are much lower (mean HQ?=?0.55), suggesting that such group is not at risk. The establishment of local and regional ingestion rates for riverine populations and market consumers is extremely recommended.     

17 β-estradiol mineralization in human waste products and soil in the presence and the absence of antimicrobials

Natural steroidal estrogens, such as 17 β-estradiol (E2), as well as antimicrobials such as doxycycline and norfloxacin, are excreted by humans and hence detected in sewage sludge and biosolid. The disposal of human waste products on agricultural land results in estrogens and antibiotics being detected as mixtures in soils. The objective of this study was to examine microbial respiration and E2 mineralization in sewage sludge, biosolid, and soil in the presence and the absence of doxycycline and norfloxacin. The antimicrobials were applied to the media either alone or in combination at total rates of 4 and 40 mg kg^?1, with the 4 mg kg^?1 rate being an environmentally relevant concentration. The calculated time that half of the applied E2 was mineralized ranged from 294 to 418 days in sewage sludge, from 721 to 869 days in soil, and from 2,258 to 14,146 days in biosolid. E2 mineralization followed first-order and the presence of antimicrobials had no significant effect on mineralization half-lives, except for some antimicrobial applications to the human waste products. At 189 day, total E2 mineralization was significantly greater in sewage sludge (38 ±0.7%) > soil (23 ±0.7%) > biosolid (3 ±0.7%), while total respiration was significantly greater in biosolid (1,258 mg CO₂) > sewage sludge (253 mg CO₂) ≥ soil (131 mg CO₂). Strong sorption of E2 to the organic fraction in biosolid may have resulted in reduced E2 mineralization despite the high microbial activity in this media. Total E2 mineralization at 189 day was not significantly influenced by the presence of doxycycline and/or norfloxacin in the media. Antimicrobial additions also did not significantly influence total respiration in media, except that total CO₂ respiration at 189 day was significantly greater for biosolid with 40 mg kg^?1 doxycycline added, relative to biosolid without antimicrobials. We conclude that it is unlikely for doxycycline and norfloxacin, or their mixtures, to have a significant effect on E2 mineralization in human waste products and soil. However, the potential for E2 to be persistent in biosolids, with and without the presence of antimicrobials, is posing a challenge for biosolid disposal to agricultural lands.     

Characterization of atmospheric aerosols by SEM in a rural area in the western part of México and its relation with different pollution sources

Samples of particulate matter were collected during the period from October 2006 through September 2007 in a rural station located 12 km from the city of Colima. A total of 3600 particles were analyzed by SEM-EDS and then classified by their chemical composition and morphology in order of abundance: those rich in C, Fe, Si–Al, Cl–Na, Ca, Ba; and to a lesser abundance, particles rich in heavy metals such as Pb and V–Ni were observed. A factorial analysis was carried out to determine the main elements related with the emission sources such as crustal/farming; fuel-oil; marine; volcanic activity and industry. Trough the seasons, the dominant winds causes the presence of anthropogenic particles in the rural site. The information presented in this study aims to give insight and detailed of the analysis of the morphological characteristics and chemical composition of atmospheric particles at individual level in a rural site from Colima State, Mexico.     

Influence of hydroxypropyl-β-cyclodextrin on the biodegradation of C-phenanthrene and C-hexadecane in soil

Soil was spiked with [9-¹⁴C]phenanthrene and [1-¹⁴C]hexadecane at 50 mg kg⁻¹ and aged for 1, 25, 50, 100 and 250 d. At each time point, the microcosms were amended with aqueous solutions of cyclodextrin (HP-β-CD) at a range of concentrations (0-40 mM). Mineralisation assays and aqueous HP-β-CD extractions were performed to assess the effect of the amendments on microbial degradation. The results showed that amendments had no significant impact on the microbial degradation of either of the ¹⁴C-contaminants. Further, HP-β-CD extractions were correlated with the mineralisation of the target chemicals in each of the soil conditions. It was found that the HP-β-CD extraction was able to predict mineralisation in soils which had not been amended with cyclodextrin; however, in the soils containing the HP-β-CD, there was no predictive relationship. Under the conditions of this study, the introduction of HP-β-CD into soils did not enhance the biodegradation of the organic contaminants.     

A retrospective study on dioxins and dioxin-like polychlorinated biphenyls in milk and dairy products from the Latium region (Italy) over a 7-year study period (2011–2017)

Environmental Science and Pollution Research - This study reports the data of polychlorinated dibenzo-p-dioxins (PCDDs), -furans (PCDFs), and polychlorinated biphenyls dioxin-like (dl PCBs)...     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.