Plant biodiversity offsets negative effects of metals and metalloids soil multi-contamination on ecosystem multifunctionality.

Despite increasing metals and metalloids (MM) human-driven soil contamination, how it simultaneously alters biodiversity and ecosystem functioning remains unknown. We used a wide gradient of a 170-year-old MM soil multi-contamination in Mediterranean scrublands to assess the effects of soil multi-contamination on multiple plant biodiversity facets, microbial communities and ecosystem multifunctionality (EMF). We found an overall positive effect of plant biodiversity on EMF mediated by microbial communities, and allowing offsetting the negative impacts of MM soil multi-contamination, especially on soil water holding capacity and nitrogen content. The diversity of distant plant lineages was the key facet promoting EMF by enhancing microbial communities, whereas the subordinate species richness altered EMF. By developing a holistic approach of these complex relationships between soil multi-contamination, plant biodiversity, microbial communities and ecosystem functioning, our results reveal the potential of plant biodiversity, and especially the diversity of evolutionary distant species, to offset the alteration of ecosystem functioning by MM soil multi-contamination. In this worldwide decade of ecosystems restoration, our study helps to identify relevant facets of plant biodiversity promoting contaminated ecosystem functioning, which is crucial to guide and optimize management efforts aiming to restore ecosystems and preserve human health.

Coronilla juncea, a native candidate for phytostabilization of potentially toxic elements and restoration of Mediterranean soils.

Soil contamination pattern due to industrial activities often leads to high concentrations of potentially toxic elements (PTE) decreasing with depth. This spatial heterogeneity of the soil contamination may have significant consequences on the soil properties and soil living communities. We evaluated the effects of both surface and solum soil contamination heterogeneity on Coronilla juncea L. (Fabaceae) functional traits in field conditions and the phytostabilization potential of this species. Plant and soil samples were collected on 3 sites along a PTE contamination gradient. The correlations between PTE concentration in plant and soil samples at 2 depths, physico-chemical properties of soil, plant biomass and soil microbial activity were tested. Field measurements highlight a decreasing PTE concentration with soil depth in addition to an important surface heterogeneity of As, Cu, Pb, Sb and Zn soil concentrations. Root PTE concentrations in C. juncea did not follow soil PTE concentrations. Concentrations of PTE in the root parts were higher than those of the aerial parts. Low PTE translocation and root symbioses with microorganisms suggest that this native plant species may play a role as engineer species with positive implications for the phytostabilization of Mediterranean PTE contaminated soils and their ecological restoration.

Underestimation of Anthropogenic Bromoform Released into the Environment?

Bromoform (CHBr3) belongs to very-short-lived substances (VSLSs), which are important precursors of reactive bromine species (BrOx) contributing to tropospheric and stratospheric chemistry. To date, most models calculating bromine product emissions to the atmosphere only consider the natural production of CHBr3 from marine organisms such as macroalgae and phytoplankton. However, CHBr3 has many other anthropogenic sources (coastal industrial sites, desalination and wastewater plants, ballast waters, and seawater toilets) that may drastically increase the amounts emitted in the atmosphere. Here, we report the levels of CHBr3 released in water and air (according to real-time and offline measurements by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography with electron capture detection (GC-ECD)) in a highly industrialized area where 3 million cubic meters of chlorinated seawater is released each day, which were measured during six field campaigns (at sea and on land) distributed over 3 years. The highest levels found during this survey (which were correlated to the physical-chemical characteristics of the water, meteorological and hydrological conditions, salinity, and temperature gradients along the water column) reached 34.6 µg L-1 in water (100-10 000 times higher than reported natural levels) and 3.9 ppbv in the air (100 times higher than the maximum reported value to date). These findings suggest the need to undertake sampling and analysis campaigns as close as possible to chlorinated discharges, as anthropogenic CHBr3 sources from industrial discharges may be a missing factor in global flux estimates or organic bromine to the atmosphere.

Functional Trait-Based Screening of Zn-Pb Tolerant Wild Plant Species at an Abandoned Mine Site in Gard (France) for Rehabilitation of Mediterranean Metal-Contaminated Soils.

The selection of plant species at mine sites is mostly based on metal content in plant parts. Recent works have proposed referring to certain ecological aspects. However, plant traits for plant metal-tolerance still need to be accurately assessed in the field. An abandoned Zn-Pb mine site in Gard (France) offered the opportunity to test a set of ecological criteria. The diversity of micro-habitats was first recorded through floristic relevés and selected categorical and measured plant traits were compared for plant species selection. The floristic composition of the study site consisted in 61 plant species from 31 plant families. This approach enabled us to focus on seven wild plant species naturally growing at the mining site. Their ability to form root symbioses was then observed with a view to phytostabilization management. Four species were considered for phytoextraction: Noccaea caerulescens (J. et C. Presl) FK Meyer, Biscutella laevigata L., Armeria arenaria (Pers.) Schult. and Plantago lanceolata L. The metal content of their aerial and root parts was then determined and compared with that of soil samples collected at the same site. This general approach may lead to the development of a knowledge base for assessment of the ecological restoration trajectory of the site and can help in plant selection for remediation of other metal-rich soils in the Mediterranean area based not only on metal removal but on ecological restoration principles.

Assessment of the ecological and human health risks from metals in shrimp aquaculture environments in Central Java, Indonesia.

The occurrence and contamination level of seven important toxic metals (Cd, Cu, Co, Cr, Hg, Pb, and Zn) and three additional metals (Al, Fe, and Mn) in the water, sediment, and shrimp muscle in aquaculture areas located in Central Java, Indonesia, were investigated. The results suggest that the majority of metals have higher concentrations in the inlet followed by the outlet and ponds. Cd dissolved in the waters exhibited the highest level in Pekalongan (3.15 ± 0.33 µg L-1). Although Pb was not detected in the water, it was detected in the sediment, and the concentration ranged from 7.6 to 15.40 mg kg-1 dw. In general, the heavy metal concentrations in the sediments were found to decrease in the sequence Al > Fe > Mn > Zn > Cr > Cu > Co > Pb. Concentrations below the effects range low level based on the Canadian sediment quality guidelines were found for Cr, Cu, Pb, and Zn, whereas moderate sediment pollution (25-75 mg kg-1 dw) was observed for Cr (all regions), Cu (except in the Pekalongan region), and Zn (Brebes and Tegal regions) according to the US EPA standard. The status of the waters was evaluated by calculating a pollution index derived mostly from Mn and Zn. The ecological risk (geoaccumulation index (Igeo), contamination factor (CF), pollution load index (PLI), and potential ecological risk index (ERI)) determined in the sediments indicated that all studied areas had low to moderate contamination. The concentrations of all metals in shrimp were generally below the maximum limits for seafood, except for Zn (in all stations), Pb, and Cr (Tegal and Pekalongan). The hazard index values for metals indicated that consuming shrimp would not have adverse effects on human health.

Assessment of water quality from the Blue Lagoon of El Cobre mine in Santiago de Cuba: a preliminary study for water reuse.

The creation of pit lakes is usually an acceptable solution from the landscaping point of view for voids left by discontinued open-pit mines. However, without rehabilitation, these voids represent a potential environmental risk. The aim of the present work was to assess, for the first time, the water quality, i.e., physicochemical characteristics, metal and metalloid (MM) content, and ecotoxicity of the waters of the El Cobre Blue Lagoon, a pit lake formed in an open-pit copper mine in Cuba. Potential effects of rainy season vs. dry season and spatial location (different depths) on water characteristics were considered. Results revealed that water contained was moderately acidic (pH = 4.6 ± 0.2), with high electrical conductivity (EC = 3.02 ± 0.03 mS cm-1), whatever the season. Dissolved oxygen (DO = 9.9 ± 2.0 mg L-1), total dissolved solid (TDS = 7003 ± 245 mg L-1), and sulfate concentration (6556 ± 1410 mg L-1) in the El Cobre Blue Lagoon water were above acceptable limits for sources of surface water as recommended by Cuban standard (NC 1021:2014). High copper (43.6 ± 1.7 mg L-1) and manganese (24.1 ± 1.1 mg L-1) contents were detected. Except for EC, sulfates, chlorides, TDS, nitrates, and phosphates, other physicochemical parameters were stable between dry and rainy seasons (p < 0.05). El Cobre Blue Lagoon waters showed an ecotoxicological impact on Vibrio fischeri. No significant differences were detected between all sampling points in the lake for each parameter monitored for a given time. These first results show the spatial homogeneity but poor quality of waters from El Cobre Blue Lagoon. Remediation processes need to be implemented in order to lessen the human and environmental health risk and favor potential water reuse. We suggest the use of constructed wetlands for water treatment. This preliminary research work can serve to alert Cuban local public authorities to the need to rehabilitate such sites.

Occurrence and speciation of chlorination byproducts in marine waters and sediments of a semi-enclosed bay exposed to industrial chlorinated effluents.

Chlorination of seawater is one of the most effective technologies for industrial biofouling control. However, chlorination leads to the formation of halogenated chlorination byproducts (CBPs) associated with potential risks to environmental and human health. The present study investigated the occurrence and distribution of CBPs in the Gulf of Fos, a semi-enclosed bay where chlorinated effluents of multiple industrial plants are discharged. Seawater samples (surface and bottom) were collected at 24 sampling stations, with some near industrial outlets and others dispersed throughout the bay. Sediment samples were also collected at 10 sampling stations. Physicochemical parameters including water temperature, pH, salinity, bromide content, and free and total residual oxidant were determined. Several chemical classes of CBPs including trihalomethanes, haloacetic acids, haloacetonitriles, trihaloacetaldehydes, and halophenols were analyzed. Bromoform was the most abundant CBP in seawater, and it was detected at most of the sampling stations of the bay with highest concentrations occurring near the industrial effluent outlets. Dibromoacetic acid was the second most abundant CBP at most of the sites followed by dibromoacetonitrile. Other detected CBPs included tribromoacetic acid, bromochloroacetonitrile, and bromal hydrate. To our knowledge, the concentration of the latter CBP was reported here for the first time in the context of industrial seawater chlorination. In sediments, two bromine-containing halophenols (2-chloro-4-bromophenol and 2,4,6-tribromophenol) were detected at two sampling stations. Ecotoxicological assays and risk assessment studies based on the detected environmental concentrations are warranted to elucidate the impacts of marine CBP contamination.

3D-printed lab-on-valve for fluorescent determination of cadmium and lead in water.

In recent years, the development of 3D printing in flow analysis has allowed the creation of new systems with various applications. Up to now, 3D printing was mainly used for the manufacture of small units such as flow detection cells, preconcentration units or mixing systems. In the present study, a new 3D printed lab-on-valve system was developed to selectively quantify lead and cadmium in water. Different technologies were compared for lab-on-valve 3D printing. Printed test units have shown that stereolithography or digital light processing are satisfactory techniques for creating complex lab-on-valve units. The lab-on-valve system was composed of two columns, eight peripheral ports and a central port, and a coil integrating baffles to increase mixing possibilities. A selective extraction of lead was first carried out by TrisKem Pb™ Resin column. Then, cadmium not retained on the first column was extracted on a second column of Amberlite® IR 120 resin. In a following step, lead and cadmium were eluted with ammonium oxalate and potassium iodide, respectively. Finally, the two metals were sequentially detected by the same Rhod-5N™ fluorescent reagent. This 3D printed lab-on-valve flow system allowed us to quantify lead and cadmium with a linear response from 0.2 to 15 µg L-1 and detection limits of 0.17 and 0.20 µg L-1 for lead and cadmium, respectively, which seems adapted for natural water analysis.

Occurrence of brominated disinfection byproducts in the air and water of chlorinated seawater swimming pools.

An undesirable consequence of disinfection is the formation of chemical contaminants known as disinfection byproducts (DBPs). Chronic exposure to DBPs has been linked to adverse health effects. The occurrence of DBPs in chlorinated pools filled with seawater (such as thalassotherapy pools and pools in spas) has received little attention so far. The present study evaluated the speciation and levels of disinfection byproducts in indoor swimming pools filled with seawater and treated with chlorine. Water and air samples were collected from three indoor swimming pools located in Southern France. Several classes of DBPs including trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetaldehydes were analyzed in water. Halogenated volatile organic compounds were analyzed in air. Extractable organic halides (EOX) contents were determined using combustion/micro-coulometry system. The speciation of DBPs identified in the three pools was predominantly brominated. The mean (arithmetic) concentration of bromoform, dibromoacetic acid, tribromoacetic acid, dibromoacetonitrile and bromal hydrate in the three pools was 79.2, 72.9, 59.9, 26.9 and 10.0µg/L, respectively. By weight, HAAs represented the most abundant chemical class followed by THMs. In air, bromoform was the most abundant THM occurring at a mean concentration of 133.2µg/m3 in the three pools. The mean EOX level was 706µgCl-/L for the three pools. In average, the quantified DBPs accounted for only 14% of EOX, thus 86% of EOX remained unknown. Further research is warranted to identify the unknown DBPs.

Exposure levels to brominated compounds in seawater swimming pools treated with chlorine.

Despite evidence of formation of brominated compounds in seawater swimming pools treated with chlorine, no data about exposure levels to these compounds have been reported. To address this issue, a survey has been carried out in four establishments (representing 8 pools) fed with seawater and devoted to relaxing and cure treatments (thalassotherapy centres located in Southeast of France). Carcinogenic and mutagenic brominated disinfection byproducts (trihalomethanes -THM- and halogenated acetic acids -HAA-) were quantified at varying levels, statistically related to organic loadings brought by bathers, and not from marine organic matter, and also linked to activities carried out in the pools (watergym vs swimming). Bromoform and dibromoacetic acid, the most abundant THM and HAA detected, were measured at levels up to 18-fold greater than the maximum contaminant levels of 60 and 80 µg/L fixed by US.EPA in drinking waters. The correlations between these disinfection byproducts and other environmental factors such as nitrogen, pH, temperature, free residual chlorine, UV(254), chloride and bromide concentrations, and daily frequentation were examined. Because thalassotherapy and seawater swimming pools (hotels, cruise ships,…) are increasing in use around the world and because carcinogenic and mutagenic brominated byproducts may be produced in chlorinated seawater swimming pools, specific care should be taken to assure cleanliness of users (swimmers and patients taking the waters) and to increase water circulation through media filters to reduce levels of brominated byproducts.

Experimental design approach for the solid-phase extraction of residual aluminium coagulants in treated waters.

Solid-phase extraction (SPE) of trace elements before their analysis has become a conventional pretreatment step of analytes because of their frequent low concentrations in numerous samples. Additionally, interfering compounds often accompagny analytes of interest, thus requiring a clean-up step. The preconcentration step and/or matrix removal can be efficiently improved by chemometric approaches allowing obtention of reliable results. Single variable approach is often used but is time and cost consuming, and may be the source of mistakes; multivariable approach allows to overcome these problems and increases the probability of global optimum finding. In order to obtain a set of experimental conditions for the selective extraction of Al(III) in water samples, onto a modified organic support (salicylic acid grafted on XAD-4), a multicriteria approach (response surface methodology) has been applied. The extraction method was optimized by the aid of a factorial design and a uniform shell Doehlert design for six variables: sample percolation flow rate, trace metal amount, sample volume, concentration and volume of HCl used for elution of aluminium. Results demonstrate the synergic effects of four factors and allow us to define working ranges for each parameter tested. The designed SPE procedure was then sucessfully applied to synthetic and real samples, issued from a potable water treatment unit.