Dissolution of mimetite Pb5(AsO4)3Cl in low-molecular-weight organic acids and EDTA

Due to its relatively low solubility, mimetite Pb₅(AsO₄)₃Cl may control Pb and As(V) solution levels at a low value in contaminated soils. The time-dependent dissolution of mimetite by low-molecular-weight organic acids (LMWOAs) such as acetic, lactic, citric, and ethylene diamine tetra-acetic acid (EDTA) was determined. At pH 3.5, the presence of citric acid or EDTA significantly increases the solubility of mimetite while acetic or lactic acids show little effect. The effect of all organic anions on the dissolution of mimetite increased with the increase in solution pH. The rate of mimetite dissolution depended on the kind and concentration of organic solvents in the sequence r_EDTA > r_lactate > r_acetate > r_citrate. Soluble Pb and As(V) released in LMWOAs and EDTA were higher than the WHO guideline value for these elements in drinking water (10 μg As(V) L⁻¹, 10 μg Pb L⁻¹). This suggests that soil organic acids in rhizosphere can potentially liberate Pb and As(V) from mimetite in contaminated soils.     

Aerobic degradation of tetrabromobisphenol-A by microbes in river sediment

This study investigated the aerobic degradation of tetrabromobisphenol-A (TBBPA) and changes in the microbial community in river sediment from southern Taiwan. Aerobic degradation rate constants (k₁) and half-lives (t_1/2) for TBBPA (50 μg g⁻¹) ranged from 0.053 to 0.077 d⁻¹ and 9.0 to 13.1 d, respectively. The degradation of TBBPA (50 μg g⁻¹) was enhanced by adding yeast extract (5 mg L⁻¹), sodium chloride (10 ppt), cellulose (0.96 mg L⁻¹), humic acid (0.5 g L⁻¹), brij 30 (55 μM), brij 35 (91 μM), rhamnolipid (130 mg L⁻¹), or surfactin (43 mg L⁻¹), with rhamnolipid yielding a higher TBBPA degradation than the other additives. For different toxic chemicals in the sediment, the results showed the high-to-low order of degradation rates were bisphenol-A (BPA) (50 μg g⁻¹) > nonylphenol (NP) (50 μg g⁻¹) > 4,4′-dibrominated diphenyl ether (BDE-15) (50 μg g⁻¹) > TBBPA (50 μg g⁻¹) > 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) (50 μg g⁻¹). The addition of various treatments changed the microbial community in river sediments. The results also showed that Bacillus pumilus and Rhodococcus ruber were the dominant bacteria in the process of TBBPA degradation in the river sediments.     

Monitoring and modelling of siloxanes in a sewage treatment plant in the UK

Monitoring of cyclic volatile methylsiloxanes (cVMS) carried out at Anglian Water’s Broadholme sewage treatment plant (STP) is described. The method deployed used headspace gas chromatography/mass spectrometry (HS-GC/MS) and the addition of isotopically labelled cVMS to correct for partitioning in samples containing high levels of particulate and dissolved organic carbon. The method was capable of measuring cVMS in raw sewage samples, with recoveries of 80%, 85% and 71% respectively, for D₄, D₅ and D₆. The limit of quantification was 0.2 μg L⁻¹ for all three substances. Recoveries close to 100% were observed for all cVMS spiked into treated effluent (LOQ = 0.01 μg L⁻¹). Despite the volatile nature of cVMS and its ubiquitous presence in the ambient atmosphere, the methods deployed showed excellent recoveries, reproducibility and quantification limits. A distinct diurnal variation in cVMS concentration, probably linked with the use of personal care products was observed for raw sewage but not in treated sewage effluent. The estimated per capita consumption of D₅ (∼2.7 mg cap⁻¹ d⁻¹) derived for the population served by this plant was significantly lower than that derived in the Environment Agency (UK) risk assessment (11.6 mg cap⁻¹ d⁻¹). The cVMS were highly removed during sewage treatment with efficiencies greater than 98%. The methods and findings of this pilot study can be used as the basis for future studies on the fate of cVMS substances in STPs.     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.     

Effects of salinity, DOM and metals on the fate and microbial toxicology of propetamphos formulations in river and estuarine sediment

Toxicity studies tend to use pure pesticides with single organisms. However, natural systems are complex and biological communities diverse. The organophosphate pesticide propetamphos (PPT) has been found exceeding regulatory limits (100 ng L⁻¹) in rivers. We address whether solution properties affect the fate of Analar (Analar-PPT) or industrial PPT (PPT-Ind) propetamphos formulations and whether propetamphos and metal toxicant effects are additive, antagonistic or synergistic? The sorption, desorption, biodegradation and microbial toxicology of Analar-PPT and PPT-Ind were investigated in Conwy River and estuary sediment. Results showed elevated salinity enhanced PPT sorption, while higher salinities increased PPT-Ind retention. Higher dissolved organic matter (DOM) and low salinity slowed Analar-PPT biodegradation (1.9 × 10⁻³ h⁻¹). Analar-PPT and PPT-Ind biodegradation was further reduced by low salinity, high DOM and dissolved Zn and Pb (6.3 × 10⁻⁴ h⁻¹, 1100 h t_½ for Analar-PPT; 7.5 × 10⁻⁴ h⁻¹, 924 h t_½ for PPT-Ind). Toxicity effects of PPT, Zn and Pb in equitoxic ratio were higher for PPT-Ind (4.7 μg PPT-Ind g⁻¹; 581 μg Zn g⁻¹; 395 μg Pb g⁻¹) than for Analar-PPT (34.6 μg PPT g⁻¹; 312 μg Zn g⁻¹; 212 μg Pb g⁻¹) whilst a toxicant ratio 1:100:10 suggested small quantities of Analar-PPT (EC₁₀ = 0.06 μg g⁻¹) affected microbial communities. The combined toxicity effect was more than additive. Thus, industrial formulations and pollutant mixtures should be considered when assessing environmental toxicity.     

Zamzam water: concentration of trace elements and other characteristics

Many Muslims drink Zamzam water for use either medicinally or religiously. Millions of pilgrims drink it and take bottles of it to their home countries. Heated scientific and political debates appeared after BBC reported in May 2011 that Zamzam water is poisonous, because of the high levels of arsenic. The World Health Organizations classifies arsenic as a human carcinogen, but some types of arsenic are also used as medicines. Adequate scientific studies on the Zamzam water are absent. This paper will provide, for the first time, basic and comprehensive information regarding the geochemical properties of Zamzam water for more than 30 indicators and using the state-of-the-art laboratory facilities. The data will help us to understand the sources of pollution under discussion, reactions at both local and international levels; and will highlight the potential healing capacity of Zamzam water. Thirty Zamzam water samples were collected by three distinct methods; from 10 pilgrims living in different locations in Germany in 2007, 10 samples from shops in Frankfurt and Berlin in 2011, and 10 samples directly from Makkah in 2011. The samples were analyzed 2 weeks after collection for more than 30 indicators: pH, EC, Eh, Cl, F, Br, NO₃, PO₄, SO₄, HCO₃, Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn beside others. Four major instruments were used; the IC, the ICPOES, the ICPMS and the HGAAS. The quality of the water did not change for 2 years and there was an excellent agreement among the results of the 30 water samples as well as between the results of the 2 years for the same samples analyzed in 2007 and 2008. The water is alkaline (average pH is 8) with an average Li concentration of 15 μg L⁻¹. The average concentrations of As and NO₃ showed values three times higher than the WHO standards (27 μg L⁻¹ and 150 mg L⁻¹, respectively). The averages of Ca and K were 95 and 50 mg L⁻¹, respectively. Very urgent steps are required to scientifically screen for the elevated parameters As, NO₃, Ca, and K in all Zamzam water sources and locations with full transparency. The resultant information should be made available to the public, and the relationship between pollution and human health should be addressed. The alkalinity of Zamzam water and the presence of trace amounts of As and Li may cause the healing power. However, a scientific strategy should be developed and adopted to enable further research and studies on toxicology and treatment technologies could be applied if needed.     

Toxic effects of chemical pesticides (trichlorfon and dimehypo) on Dunaliella salina

Dunaliella salina, a unicellular green alga of environmental tolerance, was employed as test organism to investigate the toxicity effects of trichlorfon and dimehypo widely used in agriculture and veterinary as pesticides. The influences of trichlorfon and dimehypo on cell growth, β-carotene level, cell morphology changes, and activities of superoxide dismutase (Sod) and catalase (Cat) were investigated. At the concentrations less than 0.050 g L⁻¹ trichlorfon or 0.0005 g L⁻¹ dimehypo, cell responses were similar to control. When treated with 0.075-0.100 g L⁻¹ trichlorfon or 0.001-0.004 g L⁻¹ dimehypo, cell growth and β-carotene levels declined at first and then revived. When concentrations were higher than 0.125 g L⁻¹ trichlorfon or 0.005 g L⁻¹ dimehypo, both cell growth and β-carotene levels decreased until they were undetectable. The 10-d IC50 of trichlorfon and dimehypo on D. salina were 0.179 g L⁻¹ and 0.032 g L⁻¹. Both pollutants could stimulate the increase of Cat activity at a low concentration. Tolerance of D. salina to trichlorfon was obviously higher than that of dimehypo.     

Analysis of mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs) in soil by gas chromatography tandem mass spectrometry (GC-MS/MS)

Mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs, X = Br, Cl) are formed through combustion processes, and may be more toxic than their corresponding chlorinated and brominated analogues. With 4600 potential congeners, limited analytical standards, and complex environmental matrices, PXDD/PXDFs present a significant analytical challenge. Gas chromatography tandem mass spectrometry (GC-MS/MS) offers both selectivity and sensitivity through multiple reaction monitoring of unique transitions in a novel approach to PXDD/PXDF congener identification. Method validation was performed through analysis of soil samples obtained from a recycling plant fire. Of the PXDD/PXDFs examined, monobromo-dichlorodibenzofuran was the most prevalent, ranging in concentration from 8.6 ng g⁻¹ to 180 ng g⁻¹. Dibromo-dichlorodibenzo-p-dioxin, a compound of toxicological concern, ranged from 0.41 ng g⁻¹ to 10 ng g⁻¹. Concentrations of PXDD/PXDFs were between 6% and 10% that of the corresponding polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), with the exception of dibromo-dichlorodibenzo-p-dioxin concentrations, which were 36% that of tetrachlorodibenzo-p-dioxins. Higher levels of polybrominated PXDD/PXDFs may indicate a significant bromine source was present during combustion.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

Critical Limits for Hg(II) in soils, derived from chronic toxicity data

Published chronic toxicity data for Hg(II) added to soils were assembled and evaluated to produce a data set comprising 52 chronic end-points, five each for plants and invertebrates and 42 for microbes. With end-points expressed in terms of added soil Hg(II) contents, Critical Limits were derived from the 5th percentiles of species sensitivity distributions, values of 0.13 μg (g soil)⁻¹ and 3.3 μg (g soil organic matter)⁻¹ being obtained. The latter value exceeds the currently recommended Critical Limit, used to determine Hg(II) Critical Loads in Europe, of 0.5 μg (g soil organic matter)⁻¹. We also applied the WHAM/Model VI chemical speciation model to estimate concentrations of Hg²⁺ in soil solution, and derived an approximate Critical Limit Function (CLF) that includes pH; log [Hg²⁺]_crit = −2.15 pH −17.10. Because they take soil properties into account, the soil organic matter-based limit and the CLF provide the best assessment of toxic threat for different soils. For differing representative soils, each predicts a range of up to 100-fold in the dry weight-based content of mercury that corresponds to the Critical Limit.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Removal of dissolved organic matter in municipal effluent with ozonation, slow sand filtration and nanofiltration as high quality pre-treatment option for artificial groundwater recharge

In the paper the combination process of ozonation, slow sand filtration (SSF) and nanofiltration (NF) was investigated with respect to dissolved organic matter (DOM) removal as high quality pre-treatment option for artificial groundwater recharge. With the help of ozonation leading to breakdown of the large organic molecules, SSF preferentially removes soluble microbial by-product-like substances and DOM with molecular weight (MW) less than 1.0 kDa. NF, however, removes aromatic, humic acid-like and fulvic acid-like substances efficiently and specially removes DOM with MW above 1.0 kDa. The residual DOM of the membrane permeate is dominated by small organics with MW 500 Da, which can be further reduced by the aquifer treatment, despite of the very low concentration. Consequently, the O₃/SSF/NF system offers a complementary process in DOM removal. Dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP) can be reduced from 6.5 ± 1.1 to 0.7 ± 0.3 mg L⁻¹ and from 267 ± 24 to 52 ± 6 μg L⁻¹, respectively. The very low DOC concentration of 0.6 ± 0.2 mg L⁻¹ and THMFP of 44 ± 4 μg L⁻¹ can be reached after the aquifer treatment.     

Diagnosis of dissolved organic matter removal by GAC treatment in biologically treated papermill effluents using advanced organic characterisation techniques

Granular activated carbon (GAC) exhaustion rates on pulp and paper effluent from South East Australia were found to be a factor of three higher (3.62 cf. 1.47 kg m⁻³) on Kraft mills compared to mills using Thermomechanical pulping supplemented by Recycled Fibre (TMP/RCF). Biological waste treatment at both mills resulted in a final effluent COD of 240 mg L⁻¹. The dissolved organic carbon (DOC) was only 1.2 times higher in the Kraft effluent (70 vs. 58 mg L⁻¹), however, GAC treatment of Kraft and TMP/RCF effluent was largely different on the DOC persisted after biological treatment. The molecular mass (636 vs. 534 g mol⁻¹) and aromaticity (5.35 vs. 4.67 L mg⁻¹ m⁻¹) of humic substances (HS) were slightly higher in the Kraft effluent. The HS aromaticity was decreased by a factor of 1.0 L mg⁻¹ m⁻¹ in both Kraft and TMP/RCF effluent. The molecular mass of the Kraft effluent increased by 50 g mol⁻¹ while the molecular mass of the TMP/RCF effluent was essentially unchanged after GAC treatment; the DOC removal efficiency of the GAC on Kraft effluent was biased towards the low molecular weight humic compounds. The rapid adsorption of this fraction, coupled with the slightly higher aromaticity of the humic components resulted in early breakthrough on the Kraft effluent. Fluorescence excitation-emission matrix analysis of the each GAC treated effluent indicated that the refractory components were higher molecular weight humics on the Kraft effluent and protein-like compounds on the TMP/RCF effluent. Although the GAC exhaustion rates are too high for an effective DOC removal option for biologically treated pulp and paper mill effluents, the study indicates that advanced organic characterisation techniques can be used to diagnose GAC performance on complex effluents with comparable bulk DOC and COD loads.     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

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.     

Epibrassinolide ameliorates Cr (VI) stress via influencing the levels of indole-3-acetic acid, abscisic acid, polyamines and antioxidant system of radish seedlings

The present investigation determined the effects of epibrassinolide (EBL) on the levels of indole-3-acetic acid (IAA), abscisic acid (ABA), and polyamine (PA) and antioxidant potential of 7-d old Raphanus sativus L. cv. ‘Pusa chetki’ seedlings grown under Cr (VI) metal stress. Reduced titers of free (0.767 μg g⁻¹ FW) and bound (0.545 μg g⁻¹ FW) IAA in Cr (VI) stressed seedlings were observed over untreated control. Supplementations of EBL to Cr (VI) stressed seedlings were able to enhance both free (2.14-5.68 μg g⁻¹ FW) and bound IAA (2.45-7.78 μg g⁻¹ FW) concentrations in comparison to Cr (VI) metal treatment alone. Significant rise in free (13.49 μg g⁻¹ FW) and bound (12.17 μg g⁻¹ FW) ABA contents were noticed for Cr (VI) stressed seedlings when compared to untreated control. No significant increase in ABA contents were recorded for Cr (VI) stressed seedlings upon supplementation with EBL over Cr (VI) treatment alone. A significant increase in Put (18.40 μg g⁻¹ FW) and Cad (9.08 μg g⁻¹ FW) contents were found for 10⁻⁹ M EBL plus Cr (VI) metal treatments when compared to Cr (VI) treatment alone. Spermidine (Spd) contents were found to decline significantly for EBL treatment alone or when supplemented with Cr (VI) treatments over untreated controls and Cr (VI) treatment alone. Antioxidant levels were found to enhance, with glutathione (57.98 mg g⁻¹ FW), proline (4.97 mg g⁻¹ FW), glycinebetaine (39.01 μmol mL⁻¹), ascorbic acid (3.17 mg g⁻¹ FW) and phytochelatins (65.69 μmol g⁻¹ FW) contents noted for EBL supplemented to Cr (VI) metal solution over Cr (VI) treatment alone. Reduced activities of guaiacol peroxidase (0.391 U mg⁻¹ protein) and catalase (0.221 U mg⁻¹ protein) and enhanced activities of glutathione reductase (7.14 U mg⁻¹ protein), superoxide dismutase (15.20 U mg⁻¹ protein) and ascorbate peroxidase (4.31 U mg⁻¹ protein) were observed in seedlings treated with EBL plus Cr (VI) over Cr metal treatment alone. Reduced MDA (2.55 μmol g⁻¹ FW) and H₂O₂ (33.24 μmol g⁻¹ FW) contents were recorded for 10⁻⁹ M EBL supplemented to Cr (VI) stress over Cr (VI) treatment alone. Enhancement in free radical scavenging potential as indicated by higher values of 1,1-diphenylpicrylhydrazyl, deoxyribose and reducing power activity assays, and increased levels of phenols and soluble sugars also showed significant influence of EBL in alleviating Cr (VI) stress in radish seedlings.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

Significance of analytical parameters for the understanding of natural organic matter in relation to photocatalytic oxidation

In this review, special interest was devoted to provide information on the surrogate parameters expressing both quality and quantity of organic matter for the understanding of the photocatalytic oxidation of humic substances. Detailed investigation was directed to the application of photocatalysis with reference to source, origin and modeling of organic matter. Evaluation of the literature findings emphasizes that organic matter taken from natural waters are site specific and should be characterized in detail to be comparable to other studies. Taking into account the photocatalytic degradation studies of natural organic matter, humic substances, humic acids and fulvic acids in slurry systems, a procedure could be deduced that depends on the selection of a standard model sample with a representative concentration, selection of a standard photocatalyst and dose (e.g., TiO₂ Degussa P-25, 0.25 mg mL⁻¹), application of standardized reaction conditions such as light intensity, pH, and temperature. Furthermore, standardized filtration step avoiding organic leaching and selection of the most suitable analytical parameter are the crucial points to be considered. The use of such a protocol could form a basis for the determination of “relative degradation efficiency” of any sample containing natural organic matter, humic substances, humic acids and fulvic acids regardless of dependency on source and origin.