Organochlorine pesticides in soil under irrigated cotton farming systems in Vertisols of the Namoi Valley, north-western New South Wales, Australia

Organochlorine pesticides (OCPs) such as DDT and DDE have been detected in the surface 0.2 m of Vertisols in the lower Namoi Valley of north western New South Wales, Australia even though they have not been applied to crops since 1982. However, their presence in the deeper soil horizons has not been investigated. The objective of this study was to determine if OCPs were present to a depth of 1.2 m in Vertisols under irrigated cotton farming systems in the lower Namoi Valley of New South Wales. Soil was sampled from the 0-1.2 m depths in three sites, viz. the Australian Cotton Research Institute, ACRI, near Narrabri (149°36′E, 30°12′S), and two cotton farms near Wee Waa (149°27′E, 30°13′S) and Merah North (149°18′E, 30°12′S) in northern New South Wales, Australia. The OCPs detected and their metabolites were α-endosulfan, β-endosulfan, endosulfan sulphate, DDD, DDE, DDT and endrin. The metabolite DDE, a breakdown product of DDT, was the most persistent OCP in all depths analysed. Endosulfan sulphate was the second most persistent followed by endrin > α-endosulfan > β-endosulfan > DDT and DDD. DDT was sprayed extensively in the lower Namoi Valley up to the early 1980s and may explain the persistence of DDE in the majority of soil samples. Dicofol and Dieldrin, two OCPs previously undocumented in Vertisols were also detected. The movement of OCPs into the subsoil of Vertisols may occur when irrigation or rain transports soil colloids and organic matter via preferential flow systems into the deeper layers of a soil profile. Persistence of OCPs was closely correlated to soil organic carbon concentrations. The persistence in soil of OCP’s applied to cotton crops grown more than two decades ago suggests that they could enter the food chain. Their presence at depths of 1.2 m suggests that they could move into groundwater that may eventually be used for domestic and stock consumption.     

Detection of early effects of a single herbicide (diuron) and a mix of herbicides and pharmaceuticals (diuron, isoproturon, ibuprofen) on immunological parameters of Pacific oyster (Crassostrea gigas) spat

In the context of massive summer mortality events of the Pacific oyster Crassostrea gigas, the aim of this study was to investigate the early effects on genes, enzymes and haemocyte parameters implicated in immune defence mechanisms in C. gigas oysters exposed to a potentially hostile environment, i.e. to an herbicide alone or within a mixture. Following 2 h of exposure to the herbicide diuron at 1 μg L⁻¹, the repression of different genes implicated in immune defence mechanisms in the haemocytes and the inhibition of enzyme activities, such as laccase-type phenoloxidase (PO) in the plasma, were observed. The inhibition of superoxide dismutase (SOD) activity in the plasma was also observed after 6 and 24 h of exposure. In the mixture with the herbicides diuron and isoproturon, and the pharmaceutical ibuprofen, catecholase-type PO activity in the plasma and the percentage of phagocytosis in the haemocytes were reduced after 6 h of exposure. Our results showed that early effects on molecular, biochemical and cellular parameters can be detected in the presence of diuron alone or within a mixture, giving an insight of its potential effect in situations that can be found in natural environments, i.e. relatively high concentrations for short periods of time.     

Toxicological effect of MPA-CdSe QDs exposure on zebrafish embryo and larvae

Cadmium selenium (CdSe) quantum dots (QDs) are semiconductor nanocrystals that hold wide range of applications and substantial production volumes. Due to unique composition and nanoscale properties, their potential toxicity to aquatic organisms has increasingly gained a great amount of interest. However, the impact of CdSe QDs exposure on zebrafish embryo and larvae remains almost unknown. Therefore, the lab study was performed to determine the developmental and behavioral toxicities to zebrafish under continuous exposure to low level CdSe QDs (0.05-31.25 mg L⁻¹) coated with mercaptopropionic acid (MPA). The results showed MPA-CdSe exposure from embryo to larvae stage affected overall fitness. Our findings for the first time revealed that: (1) The 120 h LC₅₀ of MPA-CdSe for zebrafish was 1.98 mg L⁻¹; (2) embryos exposed to MPA-CdSe resulted in malformations incidence and lower hatch rate; (3) abnormal vascular of FLI-1 transgenic zebrafish larvae appeared after exposure to MPA-CdSe including vascular junction, bifurcation, crossing and particle appearance; (4) larvae behavior assessment showed during MPA-CdSe exposure a rapid transition from light-to-dark elicited a similar, brief burst and a higher basal swimming rate; (5) MPA-CdSe induced embryos cell apoptosis in the head and tail region. Results of the observations provide a basic understanding of MPA-CdSe toxicity to aquatic organisms and suggest the need for additional research to identify the toxicological mechanism.     

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

Effect of microbial siderophore DFO-B on Cd accumulation by Thlaspi caerulescens hyperaccumulator in the presence of zeolite

Hyperaccumulators are grown in contaminated soil and water in order that contaminants are taken up and accumulated. Transport of metals from soil to plant is initially dependent on the solubility and mobility of metals in soil solution which is controlled by soil and metal properties and plant physiology. Complexation with organic and inorganic ligands may increase mobility and availability of metals for plants. In this work the influence of desferrioxamine-B (DFO-B), which naturally is produced in the rhizosphere, and zeolite on Cd accumulation in root and shoot of Thlaspi caerulescens (Cd hyperaccumulator) was investigated. Plants were grown in pots with clean quartz sand, amended with 1% zeolite; treatment solutions included 0, 10, and 100 μM Cd and 70 μM DFO-B. Addition of zeolite to the quartz sand significantly reduced Cd concentration in plant tissues and translocation from root to shoot. On contrary, DFO-B considerably enhanced Cd sorption by roots and translocation to aerial part of plants. Treating the plants with zeolite and DFO-B together at 10 μM Cd resulted in reduction of the bioaccumulation factor but enhancement of Cd translocation from root to shoot at the rate of 13%. In contrast, at 100 μM Cd in the solution both bioaccumulation and translocation factors decreased. Total metal accumulation as a key factor for evaluating the efficiency of phytoremediation was highly influenced by treatments. Presence of zeolite in pots significantly decreased total Cd accumulation by plants, whereas, DFO-B clearly enhanced it.     

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

Subcellular distribution and toxicity of cadmium in Potamogeton crispus L

The submerged macrophyte Potamogeton crispus L. was subjected to varying doses of cadmium (0, 20, 40, 60 and 80 μM) for 7 d, and the plants were analyzed for subcellular distribution of Cd, accumulation of mineral nutrients, photosynthesis, oxidative stress, protein content, and ultrastructural distribution of calcium (Ca). Leaf fractionation by differential centrifugation indicated that 48-69% of Cd was accumulated in the cell wall. At all doses of Cd, the levels of Ca and B rose and the level of Mn fell; the levels of Fe, Mg, Zn, Cu, Mo, and P rose initially only to decline later. Exposure to Cd caused oxidative stress as evident by increased content of malondialdehyde and decreased contents of chlorophyll and protein. Photosynthetic efficiency, as indicated by the quenching of chlorophyll a fluorescence (Fv/Fm, Fo and Fm), decreased significantly, the extent of decrease being directly proportional to the concentration of Cd. Increased amounts of precipitates of calcium were noticed in the treated plants, located either outside the cell membrane or in chloroplasts, mitochondria, the nucleus, and the cytoplasm whereas control plants showed small deposits of the precipitates around surface of the vacuole membrane and in the intercellular space but rarely in the cytoplasm. Photosynthetic efficiency and oxidative stress could be used as indicators of physiological end-points in determining the extent of Cd phytotoxicity.     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.