Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater

Biocide-containing anti-fouling paints are regulated and approved according to the added active ingredients, such as Cu. Biocide-free paints are considered to be less environmentally damaging and do not need an approval. Zn, a common ingredient in paints with the potential of causing adverse effects has received only minor attention. Laboratory experiments were conducted in artificial brackish seawater (ASW) and natural brackish seawater (NSW) to quantify release rates of Cu and Zn from biocide-containing and biocide-free labeled eroding anti-fouling paints used on commercial vessels as well as leisure boats. In addition, organisms from three trophic levels, the crustacean Nitocra spinipes, the macroalga Ceramium tenuicorne and the bacteria Vibrio fischeri, were exposed to Cu and Zn to determine the toxicity of these metals. The release rate of Cu in NSW was higher from the paints for professional use (3.2-3.6 µg cm⁻² d^− 1) than from the biocide leaching leisure boat paint (1.1 µg cm⁻² d^− 1). Biocide-free paints did leach considerably more Zn (4.4-8.2 µg cm⁻² d^− 1) than biocide-containing leisure boat paint (3.0 µg cm⁻² d^− 1) and ship paints (0.7-2.0 µg cm⁻² d^− 1). In ASW the release rates of both metals were notably higher than in NSW for most tested paints. The macroalga was the most sensitive species to both Cu (EC₅₀ = 6.4 µg l^− 1) and Zn (EC₅₀ = 25 µg l^− 1) compared to the crustacean (Cu, LC₅₀ = 2000 µg l^− 1 Zn, LC₅₀ = 890 µg l^− 1), and the bacteria (Cu, EC₅₀ = 800 µg l^− 1 and Zn, EC₅₀ = 2000 µg l^− 1). The results suggest that the amounts of Zn and Cu leached from anti-fouling paints may attain toxic concentrations in areas with high boat density. To fully account for potential ecological risk associated with anti-fouling paints, Zn as well as active ingredients should be considered in the regulatory process.     

Temporal variations in arsenic uptake by rice plants in Bangladesh: The role of iron plaque in paddy fields irrigated with groundwater

The transfer of arsenic to rice grains is a human health issue of growing relevance in regions of southern Asia where shallow groundwater used for irrigation of paddy fields is elevated in As. In the present study, As and Fe concentrations in soil water and in the roots of rice plants, primarily the Fe plaque surrounding the roots, were monitored during the 4-month growing season at two sites irrigated with groundwater containing ∼ 130 μg l^− 1 As and two control sites irrigated with water containing < 15 μg l^− 1 As. At both sites irrigated with contaminated water, As concentrations in soil water increased from < 10 μg l^− 1 to > 1000 μg l^− 1 during the first five weeks of the growth season and then gradually declined to < 10 μg l^− 1 during the last five weeks. At the two control sites, concentrations of As in soil water never exceeded 40 µg l^− 1. At both contaminated sites, the As content of roots and Fe plaque rose to 1000-1500 mg kg^− 1 towards the middle of the growth season. It then declined to ∼ 300 mg kg^− 1 towards the end, a level still well above As concentration of ∼ 100 mg kg^− 1 in roots and plaque measured throughout the growing season at the two control sites. These time series, combined with simple mass balance considerations, demonstrate that the formation of Fe plaque on the roots of rice plants by micro-aeration significantly limits the uptake of As by rice plants grown in paddy fields. Large variations in the As and Fe content of plant stems at two of the sites irrigated with contaminated water and one of the control sites were also recorded. The origin of these variations, particularly during the last month of the growth season, needs to be better understood because they are likely to influence the uptake of As in rice grains.     

DDT contamination from indoor residual spraying for malaria control

The insecticide DDT is still used in specific areas of South Africa for indoor residual spray (IRS) to control malaria vectors. Local residents could be exposed to residues of DDT through various pathways including indoor air, dust, soil, food and water. The aims of this study were to determine the levels of DDT contamination, as a result of IRS, in representative homesteads, and to evaluate the possible routes of human exposure. Two villages, exposed (DV) and reference (TV) were selected. Sampling was done two months after the IRS process was completed. Twelve homesteads were selected in DV and nine in TV. Human serum, indoor air, floor dust, outside soil, potable water, leafy vegetables, and chicken samples (muscle, fat and liver) were collected and analyzed for both the o,p′- and p,p′-isomers of DDT, DDD and DDE. DDT was detected in all the media analyzed indicating a combination of potential dietary and non-dietary pathways of uptake. DV had the most samples with detectable levels of DDT and its metabolites, and with the exception of chicken muscle samples, DV also had higher mean levels for all the components analyzed compared to TV. Seventy-nine percent of participants from DV had serum levels of DDT (mean ∑ DDT 7.3 µg g⁻¹ lipid). These residues constituted mainly of p,p′-DDD and p,p′-DDE. ∑ DDT levels were detected in all indoor air (mean ∑ DDT 3900.0 ng m^− 3) and floor dust (mean ∑ DDT 1200.0 µg m^− 2) samples. Levels were also detected in outside soil (mean ∑ DDT 25.0 µg kg^− 1) and potable water (mean ∑ DDT 2.0 µg L^− 1). Vegetable sample composition (mean ∑ DDT 43.0 µg kg^− 1) constituted mainly p,p′-DDT and p,p′-DDD. Chicken samples were highly contaminated with DDT (muscle mean ∑ DDT 700.0 µg kg^− 1, fat mean ∑ DDT 240,000.0 µg kg^− 1, liver mean ∑ DDT 1600.0 µg kg^− 1). The results of the current study raise concerns regarding the potential health effects in residents living in the immediate environment following DDT IRS.     

Water, vegetation and sediment gradients in submerged aquatic vegetation mesocosms used for low-level phosphorus removal

Gradients in phosphorus (P) removal and storage were investigated over 6 years using mesocosms (each consisting of three tanks in series) containing submerged aquatic vegetation (SAV) grown on muck and limerock (LR) substrates. Mean inflow total P concentrations (TP) of 32 μg L⁻¹ were reduced to 15 and 17 μg L⁻¹ in the muck and LR mesocosms, respectively. Mesocosm P loading rates (mean = 1.75 g m⁻² year⁻¹) varied widely during the study and were not correlated with outflow TP, which instead varied seasonally with lowest monthly mean values in December and January.The mesocosms initially were stocked with Najas guadalupensis, Ceratophyllum demersum, and Chara zeylanica, but became dominated by C. zeylanica. At the end of the study, highest vegetative biomass (1.1 and 1.4 kg m⁻² for muck and LR substrates) and tissue P content (1775 and 1160 mg kg⁻¹) occurred in the first tank in series, and lowest biomass (1.0 and 0.2 kg m⁻²) and tissue P (147 and 120 mg kg⁻¹) in the third tank. Sediment accretion rates (2.5, 1.9 and 0.9 cm yr⁻¹ on muck substrates), accrued sediment TP (378, 309 and 272 mg kg⁻¹), and porewater soluble reactive P (SRP) concentrations (40, 6 and 4 μg L⁻¹) in the first, second and third tanks, respectively, exhibited a similar decreasing spatial trend. Plant tissue calcium (Ca) near mesocosm inflow (19-30% dry weight) and outflow (23-26%) were not significantly different, and sediment Ca was also similar (range of 24 to 28%) among sequential tanks.Well-defined vegetation and sediment enrichment gradients developed in SAV wetlands operated under low TP conditions. While the mesocosm data did not reflect deterioration in treatment performance over 6 years, accumulation of P-enriched sediments near the inflow could eventually compromise hydraulic storage and P removal effectiveness of these shallow systems.     

Influence of initial pesticide concentrations and plant population density on dimethomorph toxicity and removal by two duckweed species

Aquatic plants take up, transform and sequester organic contaminants and may therefore be used in phytoremediation for the removal of pollutants from wastewaters. A better understanding of factors affecting the rate of contaminant uptake by aquatic plants is needed to improve engineered systems for removal of pollutants from wastewaters. This work focused on the influence of initial concentrations of pesticide and population density of plants on toxicity and uptake of the fungicide dimethomorph by two duckweed species. An increased sensitivity to dimethomorph was observed with increasing duckweed population density. Less light, due to crowding, may explain this higher sensitivity and reduced removal rate. A positive relationship was also found between toxicity or contaminant uptake and initial pesticide concentration with a maximal removal of 41 and 26 µg g^− 1 fresh weight of dimethomorph (at 600 µg L^− 1 of dimethomorph and an initial density of 0.10 g E-flask^− 1) by Lemna minor and Spirodela polyrhiza, respectively. This research also indicated that these aquatic plants can efficiently eliminate organic contaminants and may ultimately serve as phytoremediation agents in the natural environment.     

Plant tolerance to diesel minimizes its impact on soil microbial characteristics during rhizoremediation of diesel-contaminated soils

Soil contamination due to petroleum-derived products is an important environmental problem. We assessed the impacts of diesel oil on plants (Trifolium repens and Lolium perenne) and soil microbial community characteristics within the context of the rhizoremediation of contaminated soils. For this purpose, a diesel fuel spill on a grassland soil was simulated under pot conditions at a dose of 12,000 mg diesel kg^− 1 DW soil. Thirty days after diesel addition, T. repens (white clover) and L. perenne (perennial ryegrass) were sown in the pots and grown under greenhouse conditions (temperature 25/18 °C day/night, relative humidity 60/80% day/night and a photosynthetic photon flux density of 400 μmol photon m^− 2 s^− 1) for 5 months. A parallel set of unplanted pots was also included. Concentrations of n-alkanes in soil were determined as an indicator of diesel degradation. Seedling germination, plant growth, maximal photochemical efficiency of photosystem II (F_v/F_m), pigment composition and lipophylic antioxidant content were determined to assess the impacts of diesel on the studied plants. Soil microbial community characteristics, such as enzyme and community-level physiological profiles, were also determined and used to calculate the soil quality index (SQI). The presence of plants had a stimulatory effect on soil microbial activity. L. perenne was far more tolerant to diesel contamination than T. repens. Diesel contamination affected soil microbial characteristics, although its impact was less pronounced in the rhizosphere of L. perenne. Rhizoremediation with T. repens and L. perenne resulted in a similar reduction of total n-alkanes concentration. However, values of the soil microbial parameters and the SQI showed that the more tolerant species (L. perenne) was able to better maintain its rhizosphere characteristics when growing in diesel-contaminated soil, suggesting a better soil health. We concluded that plant tolerance is of crucial importance for the recovery of soil health during rhizoremediation of contaminated soils.     

Organochlorine pesticides, polychlorinated biphenyls and trace elements in wild European sea bass (Dicentrarchus labrax) off European estuaries

Polychlorinated biphenyls (PCBs) and organochlorine pesticides like dichloro-diphenyl-trichloroethane (DDTs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin and trace elements (Cd, Cu, Se, Pb, Zn and Hg) were analysed in the muscle of European sea bass (Dicentrarchus labrax) sampled in Atlantic coastal regions near several important European river mouths (Gironde, Charente, Loire, Seine and Scheldt). High contamination levels were measured in the muscles of European sea bass sampled in the coastal regions near those river mouths (e.g. Σ ICES PCB = 133-10,478 μg kg^− 1 lw and Hg = 250-2000 μg kg^− 1 dw).The Scheldt and the Seine are still among the most contaminated estuaries in Europe. Each region presented their specific contamination patterns reflecting different sources due to the input of the respective rivers. As fish and fishery products are the main contributors of the total dietary intake of organochlorinated pollutants, regular consumption of European sea bass with the reported contamination levels may represent a significant exposure route for the general human population.     

Rhizosphere characteristics of two arsenic hyperaccumulating Pteris ferns

Better understanding of the processes controlling arsenic bioavailability in the rhizosphere is important to enhance plant arsenic accumulation by hyperaccumulators. This greenhouse experiment was conducted to evaluate the chemical characteristics of the rhizosphere of two arsenic hyperaccumulators Pterisvittata and Pterisbiaurita. They were grown for 8 weeks in rhizopots containing arsenic-contaminated soils (153 and 266 mg kg^− 1 arsenic). Bulk and rhizosphere soil samples were analyzed for water-soluble As (WS-As) and P (WS-P), pH, and dissolved organic carbon (DOC). Comparing the two plants, P.vittata was more tolerant to arsenic and more efficient in arsenic accumulation than P.biaurita, with the highest frond arsenic being 3222 and 2397 mg kg^− 1. Arsenic-induced root exudates reduced soil pH (by 0.74-0.92 units) and increased DOC concentrations (2-3 times) in the rhizosphere, resulting in higher WS-P (2.6-3.8 times higher) compared to the bulk soil. Where there was no difference in WS-As between the rhizosphere and bulk soil in soil-153 for both plants, WS-As in the rhizosphere was 20-40% higher than those in bulk soil in soil-266, indicating that the rate of As-solubilization was more rapid than that of plant uptake. The ability to solubilize arsenic via root exudation in the rhizosphere and the ability to accumulate more P under arsenic stress may have contributed to the efficiency of hyperaccumulator plants in arsenic accumulation.     

Selenium concentrations of common weeds and agricultural crops grown in the seleniferous soils of northwestern India

The plants grown in seleniferous soils constitute a major source of toxic selenium levels in the food chain of animals and human beings. Greenhouse and field experiments were conducted to study selenium concentrations of weeds, forages and cereals grown on seleniferous soils located between 31.0417° to 31.2175° N and 76.1363° to 76.4147° E in northwestern India. Eleven winter season (November-April) weed plants were grown in the greenhouse in a soil treated with different levels of selenate-Se. Selenium concentrations of weed plants increased progressively with the levels of selenate-Se in soil. The highest Se concentration was recorded by Silene gallica (246 mg kg^− 1) and the lowest by Avena ludoviciana (47 mg kg^− 1) at 2.5 mg Se kg^− 1 soil. A.ludoviciana and Spergula arvensis proved highly tolerant to the presence of 1.25 and 2.5 mg selenate-Se kg^− 1 soil and the remaining weeds were sensitive to Se. Dry matter yield of Se-sensitive weed plants was 25 to 62% of the yield in the no-Se control at 1.25 mg selenate-Se kg^− 1 and 6 to 40% at 2.5 mg selenate-Se kg^− 1 soil. Other symptoms like change in leaf colour and size, burning of leaf tips and margins, and delayed flowering were also observed due to Se. Dry matter yield of Se-sensitive weed plants expressed as percentage of yield in the no-Se control at both the Se levels was inversely correlated with their Se content (r = − 0.731, p < 0.01, N = 17). Among the weed plants grown in seleniferous soils under field situations, Mentha longifolia accumulated the highest Se (365 mg kg^− 1) and Phalaris minor the lowest (34 mg kg^− 1). Among agricultural crops grown on a naturally contaminated soil in the greenhouse, Se concentrations were the highest for oilseed crops (19-29 mg kg^− 1), followed by legumes (6-13 mg kg^− 1) and cereals (2-18 mg kg^− 1). Helianthus annuus among the oilseed crops, A.ludoviciana among the winter season weeds, M.longifolia among the summer season (May-October) weeds and Cirsium arvense among the perennial weeds can be used for phytoremediation of seleniferous soils as these accumulate the highest amounts of Se.     

Impact of toxic cyanobacteria on gastropods and microcystin accumulation in a eutrophic lake (Grand-Lieu, France) with special reference to Physa (= Physella) acuta

Hepatotoxic microcystins (MCs) produced by cyanobacteria are known to accumulate in gastropods following grazing of toxic cyanobacteria and/or absorption of MCs dissolved in water, with adverse effects on life history traits demonstrated in the laboratory. In the field, such effects may vary depending on species, according to their relative sensitivity and ecology. The aims of this study were to i) establish how various intensities of MC-producing cyanobacteria proliferations alter the structure of gastropod community and ii) compare MC tissue concentration in gastropods in the field with those obtained in our previous laboratory experiments on the prosobranch Potamopyrgus antipodarum and the pulmonate Lymnaea stagnalis. We explored these questions through a one-year field study at three stations at Grand-Lieu Lake (France) affected by different intensities of cyanobacteria proliferations. A survey of the community structure and MC content of both cyanobacteria and gastropods was associated with a caging experiment involving P. antipodarum and L. stagnalis. In total, 2592 gastropods belonging to 7 prosobranch and 16 pulmonate species were collected. However, distribution among the stations was unequal with 62% vs 2% of gastropods sampled respectively at the stations with the lowest vs highest concentrations of MC. Irrespective of the station, pulmonates were always more diverse, more abundant and occurred at higher frequencies than prosobranchs. Only the pulmonate Physa acuta occurred at all stations, with abundance and MC tissue concentration (≤ 4.32 µg g DW^− 1) depending on the degrees of MC-producing cyanobacteria proliferations in the stations; therefore, P. acuta is proposed as a potential sentinel species. The caging experiment demonstrated a higher MC accumulation in L. stagnalis (≤ 0.36 µg g DW^− 1 for 71% of individuals) than in P. antipodarum (≤ 0.02 µg g DW^− 1 for 12%), corroborating previous laboratory observations. Results are discussed in terms of differential gastropod sensitivity and MC transfer through the food web.     

The intake of lead and associated metals by sheep grazing mining-contaminated floodplain pastures in mid-Wales, UK: II. Metal concentrations in blood and wool

Sheep grazing metal-contaminated floodplain pastures across mid-Wales ingest high concentrations of lead (Pb) in vegetation and directly in the form of soil. Sheep whole blood analysis indicated that Pb concentrations can be significantly elevated for animals grazing contaminated sites: in winter/spring, a median blood concentration of 147 µg Pb l^− 1 was found at the location with the highest soil enrichment of this metal compared to only 26 µg Pb l^− 1 for the control flock. There was within-flock variability in blood-Pb concentration, and overlap between blood-Pb ranges in animals grazing control and contaminated sites, although use of the Kruskal-Wallis H test established a number of significant (P < 0.05) differences between the blood-Pb content of flocks grazing the various study locations. Despite total daily intakes of up to 723 mg Pb d^− 1, only one individual sheep showed a blood-Pb content above the ‘normal safe’ concentration of 250 µg l^− 1. Blood and wool analyses were found to have limited value for the diagnosis of environmental exposure to Pb, and further consideration of metal accumulation in offal, bone and muscle tissue is recommended.     

Accumulation of oxytetracycline and norfloxacin from saline soil by soybeans

Soil of former shrimp aquaculture facilities in Thailand may be contaminated by antibiotics (e.g. oxytetracycline and norfloxacin) and have elevated salinity. Therefore, reuse of this land can be problematic. The utility of soybean (Glycine max (L.) Merr.) for phytoremediation was investigated. The rate of germination and seedling emergence in prepared contaminated soil (conductivity 17.7 dS m^− 1 from adding 70 mg sodium chloride g^− 1 dry weight, 105 mg kg^− 1 dry weight oxytetracycline and 55 mg kg^− 1 dry weight norfloxacin) in sunlight was approximately 80% that of uncontaminated soil. This reduction was largely due to the high salinity. The antibiotics of interest degraded relatively rapidly in soil (half-life < 10 h for both) but loss was slower in deionised water. Accumulation of the antibiotics from deionised water by soybean resulted in little effect on growth rate and maximum levels in plants were observed after two days exposure, followed by declining concentrations. For soybean plants grown in saline soil, 90% removal of NaCl from soil adjacent to plant roots was observed, most within two days. Wilting and defoliation occurred, but plants recovered after 10 days and maximum salt levels in plants exceeded 20,000 mg g^− 1 dry weight with translocation from root to shoot tissue noted. Soybean plants also accumulated the antibiotics from prepared contaminated saline soil, but translocation from the roots was not observed. The results showed that soybean can be valuable for phytoremediation in these situations.     

Interactions between selected PAHs and the microbial community in rhizosphere of a paddy soil

This study investigated the interaction of three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene (NAP), phenanthrene (PHN), and pyrene (PYR), with the microbial community in the rhizosphere of a paddy soil and the influence of the rice (Oryza sativa) rhizosphere on the microbial community structure. A range of initial NAP, PHN and PYR levels in soil (50-200, 18-72, and 6.6-26.6 mg kg^− 1, respectively) were prepared and the soil samples were then aged for 4 months (to yield PAH concentrations at 1.02-1.42, 1.32-4.77, and 2.98-18.5 mg kg^− 1, respectively) before the soil samples were planted with rice seedlings. The microbial phospholipid-fatty-acid (PLFA) patterns in PAH-contaminated soils were analyzed to elucidate the changes of the microbial biomass and community composition. Results indicated that at the applied concentrations the PAHs were not toxic to rice seedlings, as evidenced by no growth inhibition during the 8-week planting period. However, the microbial biomass, as revealed by PLFAs, decreased significantly with increasing PAH concentration in both rhizospheric and non-rhizospheric soils. The PAHs in soils were obviously toxic to microorganisms, and the toxicity of PHN was greater than PYR due likely to the higher PHN bioavailability. Total PLFAs in rhizospheric soils were profoundly higher than those in non-rhizospheric soils, suggesting that the inhibitive effect of PAHs on microbial activities was alleviated by the rice roots. The principal component analysis (PCA) of the PLFA signatures revealed pronounced changes in PLFA pattern in rhizospheric and non-rhizospheric soils with or without spiked PAHs. Using the PLFA patterns as a biomarker, it was found that Gram-positive bacteria were more sensitive to PAHs than Gram-negative bacteria, and the rhizosphere of rice roots stimulated the growth of aerobic bacteria.     

Mercury contamination in the vicinity of a chlor-alkali plant and potential risks to local population

A mercury-cell chlor-alkali plant operated in Estarreja (North-western Portugal) for 50 years causing widespread environmental contamination. Although production by this process ceased in 2002, mercury contamination from the plant remains significant. The main objective of this study was to investigate mercury impact on the nearby environment and potential risks to local population. To assess the level of contamination soil samples were collected from agricultural fields in the vicinity of the plant, extending the study by taking samples of the predominant vegetation suitable for animal and human consumption, water samples, and fish species from a nearby coastal lagoon, to gain a preliminary insight into the potential for contamination of the terrestrial and aquatic food web. To determine population exposure to mercury, hair samples were collected from local residents. Total mercury concentration in the 0-15 cm layer of soil was found to be highly variable, ranging between 0.010 and 91 mg kg^− 1, although mercury contamination of soils was found to be restricted to a confined area. Lolium perenne roots contained between 0.0070 and 2.0 mg kg^− 1, and there is evidence that root systems uptake mercury from the soil. Levels of mercury in the aerial parts of plants ranged between 0.018 and 0.98 mg kg^− 1. It appears that plants with higher mercury concentration in soils and roots also display higher mercury concentration in leaves.Total mercury concentration in water samples ranged between 12 and 846 ng L^− 1, all samples presenting concentrations below the maximum level allowable for drinking water defined in the Portuguese law (1.0 μg L^− 1).Mercury levels in fish samples were below the maximum limit defined in the Portuguese law (0.5 mg kg^− 1), ranging from 0.0040 to 0.24 mg kg^− 1. Vegetables collected presented maximum mercury concentration of 0.17 mg kg^− 1. In general, food is not contaminated and should not be responsible for major human exposure to the metal.Mercury determined in human hair samples (0.090-4.2 mg kg^− 1; mean 1.5 mg kg^− 1) can be considered within normal limits, according to WHO guidelines suggesting that it is not affecting the local population. Despite being subject to decades of mercury emissions, nowadays this pollutant is only found in limited small areas and must not constitute a risk for human health, should these areas be restricted and monitored.Considering the present data, it appears that the population from Estarreja is currently not being affected by mercury levels that still remain in the environment.     

Influence of soil properties on trace element availability and plant accumulation in a Mediterranean salt marsh polluted by mining wastes: implications for phytomanagement

The aims of this study were to determine the factors which control metal and As phytoavailability in the different microenvironments (Sand Dunes, Salt Flat, Dry River and Shrubs) present at a Mediterranean salt marsh polluted by mining wastes. We performed a field study following a plot sampling survey. The analyses of soil parameters (pH, electrical conductivity (EC), organic carbon contents, etc.), total metal and As concentrations and their phytoavailability assessed with EDTA were related to each microenvironment and the corresponding plant species uptake. The averages of pH and EC were slightly alkaline (pH ≈ 7.5) and saline (≈ 2.2 to 17.1 dS m⁻¹) respectively. The soil samples from the Salt Flat subzone showed the highest metal concentrations (e.g. 51 mg kg⁻¹ Cd, 11,600 mg kg⁻¹ Pb) while for As, the highest concentrations occurred in the Dry River (380 mg kg⁻¹ As). The total metal and EDTA-extractable concentrations occurred as it follows: Salt Flat > Dry River > Degraded Dunes > Shrubs. In relation to plant metal and As accumulation, the highest root concentrations were obtained in the species from the Salt Flat subzone: ~ 17 mg kg⁻¹ As, ~ 620 mg kg⁻¹ Pb, for both, Juncus maritimus and Arthrocnemum macrostachyum. However the highest metal and As shoot concentrations occurred in species from the Sand Dunes: ~ 23 mg kg⁻¹ As ~ 270 mg kg⁻¹ Pb for Dittrichia viscosa; ~ 23 mg kg⁻¹ As, ~ 390 mg kg⁻¹ Zn for Crucianella maritima. The occurrence of edaphic gradients including salinity and texture determined the vegetation distribution. However, it cannot be concluded that there was a disturbance due to metal(loid)s soil concentrations in terms of vegetation composition except in the Degraded Dunes and Dry River. The higher EDTA-extractable concentrations were coincidental with the most saline soils but this did not result in higher metal(loid)s plant accumulation.     

Phytotoxicity and uptake of nitroglycerin in a natural sandy loam soil

Nitroglycerin (NG) is widely used for the production of explosives and solid propellants, and is a soil contaminant of concern at some military training ranges. NG phytotoxicity data reported in the literature cannot be applied directly to development of ecotoxicological benchmarks for plant exposures in soil because they were determined in studies using hydroponic media, cell cultures, and transgenic plants. Toxicities of NG in the present studies were evaluated for alfalfa (Medicago sativa), barnyard grass (Echinochloa crusgalli), and ryegrass (Lolium perenne) exposed to NG in Sassafras sandy loam soil. Uptake and degradation of NG were also evaluated in ryegrass. The median effective concentration values for shoot growth ranged from 40 to 231 mg kg^− 1 in studies with NG freshly amended in soil, and from 23 to 185 mg kg^− 1 in studies with NG weathered-and-aged in soil. Weathering-and-aging NG in soil did not significantly affect the toxicity based on 95% confidence intervals for either seedling emergence or plant growth endpoints. Uptake studies revealed that NG was not accumulated in ryegrass but was transformed into dinitroglycerin in the soil and roots, and was subsequently translocated into the ryegrass shoots. The highest bioconcentration factors for dinitroglycerin of 685 and 40 were determined for roots and shoots, respectively. Results of these studies will improve our understanding of toxicity and bioconcentration of NG in terrestrial plants and will contribute to ecological risk assessment of NG-contaminated sites.     

Nitrogen transformations and greenhouse gas emissions from a riparian wetland soil: an undisturbed soil column study

Riparian wetlands bordering intensively managed agricultural fields can act as biological filters that retain and transform agrochemicals such as nitrate and pesticides. Nitrate removal in wetlands has usually been attributed to denitrification processes which in turn imply the production of greenhouse gases (CO₂ and N₂O). Denitrification processes were studied in the Salburua wetland (northern Spain) by using undisturbed soil columns which were subsequently divided into three sections corresponding to A-, Bg- and B2g-soil horizons. Soil horizons were subjected to leaching with a 200 mg NO₃⁻ L^− 1 solution (rate: 90 mL day^− 1) for 125 days at two different temperatures (10 and 20 °C), using a new experimental design for leaching assays which enabled not only to evaluate leachate composition but also to measure gas emissions during the leaching process. Column leachate samples were analyzed for NO₃⁻ concentration, NH₄⁺ concentration, and dissolved organic carbon. Emissions of greenhouse gases (CO₂ and N₂O) were determined in the undisturbed soil columns. The A horizon at 20 °C showed the highest rates of NO₃⁻ removal (1.56 mg N-NO₃⁻ kg⁻¹ DW soil day^− 1) and CO₂ and N₂O production (5.89 mg CO₂ kg⁻¹ DW soil day^− 1 and 55.71 μg N-N₂O kg⁻¹ DW soil day^− 1). For the Salburua wetland riparian soil, we estimated a potential nitrate removal capacity of 1012 kg N-NO₃⁻ ha^− 1 year^− 1, and potential greenhouse gas emissions of 5620 kg CO₂ ha^− 1 year^− 1 and 240 kg N-N₂O ha^− 1 year^− 1.     

Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bioreactors

Concern is growing over contamination of the environment with pharmaceuticals because of their widespread use and incomplete removal during wastewater treatment, where microorganisms drive the key processes. The influence of pharmaceuticals on bacterial community structure in activated sludge was assessed in small-scale wastewater treatment bioreactors containing different concentrations (5, 50, 200 and 500 μg L⁻¹) of several commonly used pharmaceuticals (ibuprofen, naproxen, ketoprofen, diclofenac and clofibric acid). T-RFLP analyses of the bacterial 16S rRNA genes indicated a minor but consistent shift in the bacterial community structure in the bioreactor R50 supplied with pharmaceuticals at a concentration of 50 μg L⁻¹, compared to the control reactor R0, which was operated without addition of pharmaceuticals. In the reactors operated with higher concentrations of pharmaceuticals, a greater structural divergence was observed. Bacterial community composition was further investigated by preparation of two clone libraries of bacterial 16S rRNA genes from reactors R0 and R50. Most clones in both libraries belonged to the Betaproteobacteria, among which Thauera, Sphaerotilus, Ideonella and Acidovorax-related spp. dominated. Nitrite-oxidizing bacteria of the genus Nitrospira sp., which are key organisms for the second stage of nitrification in wastewater treatment plants, were found only in the clone library of the reactor without pharmaceuticals. In addition, diversity indices were calculated for the two clone libraries, indicating a reduced diversity of activated sludge bacterial community in the reactor supplied with 50 μg L⁻¹ of each of selected pharmaceuticals.     

Assessing the risk posed to free-living soil nematodes by a genetically modified maize expressing the insecticidal Cry3Bb1 protein

Before pest-resistant genetically modified maize can be grown commercially, the risks for soil-beneficial, non-target organisms must be determined. Here, a tiered approach was used to assess the risk to free-living soil nematodes posed by maize genetically modified to express the insecticidal Cry3Bb1 protein (event Mon88017), which confers resistance towards western corn rootworm (Diabrotica virgifera; Coleoptera). The toxicity of purified Cry3Bb1 for the nematode Caenorhabditis elegans was determined using a bioassay and gene expression analysis. In addition, a soil toxicity test was used to assess the effects on C. elegans of rhizosphere soil obtained from plots of an experimental field grown with Mon88017, the near-isogenic cultivar, or either of two conventional cultivars. Finally, the indigenous nematode communities from the experimental field site with Mon88017 and from the control cultivars were analyzed. The results showed a dose-dependent inhibitory effect of Cry3Bb1 on the growth and reproduction of C. elegans, with EC50 values of 22.3 mg l⁻¹ and 7.9 mg l⁻¹, respectively. Moreover, Cry-protein-specific defense genes were found to be up-regulated in the presence of either Cry1Ab or Cry3Bb1. However, C. elegans was not affected by rhizosphere soils from Mon88017 compared to the control plots, due to the very low Cry3Bb1 concentrations, as indicated by quantitative analyses (< 1 ng g⁻¹ soil). Nematode abundance and diversity were essentially the same between the various maize cultivars. At the last sampling date, nematode genus composition in Bt-maize plots differed significantly from that in two of the three non-Bt cultivars, including the near-isogenic maize, but the shift in genus composition did not influence the composition of functional guilds within the nematode communities. In conclusion, the risk to free-living soil nematodes posed by Mon88017 cultivation can be regarded as low, as long as Cry3Bb1 concentrations in soil remain four orders of magnitude below the toxicity threshold.     

Evidences of non-reactive mercury-selenium compounds generated from cultures of Pseudomonas fluorescens

This work was designed to determine chemically inert mercury-selenium (Hg-Se) compounds formed in a culture of Pseudomonas fluorescens exposed to Hg²⁺ and Se^IV (selenite). To isolate these compounds, different digestion methods were studied and sodium dodecyl sulfate (SDS) lysis was selected. The Hg⁰ and non-reactive Hg were determined in two series of cultures containing 0.0-6.00 μg L⁻¹ Se^IV (0.0-76.0 μmol L⁻¹) in combination with low 5.00 μg L⁻¹ (0.025 μmol L⁻¹) or high 100 μg L⁻¹ (0.500 μmol L⁻¹) Hg²⁺. It was found that Hg⁰ formed in the culture decreased with the increase of initial Se^IV, while the non-reactive Hg increased with the Se^IV. In cultures with low initial [Hg²⁺], a median Se^IV (2.0 μg L⁻¹ or 25.3 μmol L⁻¹) resulted in about 70% of the added Hg²⁺ sequestered as non-reactive Hg, and in culture with high initial Hg²⁺, about 40% was sequestered. P. fluorescens was proved to be indispensible for the formation of the non-reactive Hg-Se compounds. The Hg:Se molar ratio in the non-reactive Hg-Se compounds was close to 1, suggesting the existence of mercuric selenide in cells. Mechanisms for the formation of the non-reactive Hg-Se compounds are proposed.