Substance-related environmental monitoring

Background  Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on ‘Environmental Monitoring’ of the Division of ‘Environmental Chemistry and Ecotoxicology’ within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope  Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives  An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

Evaluation of effectiveness of EDTA and sodium thiosulfate in removing metal toxicity toward sea urchin embryo-larval applying the TIE

Since the development of the TIE (Toxicity Identification and Evaluation) in 1988 it has been assumed that the capacity of EDTA and sodium thiosulfate to complex some metals, and thus remove their toxicity, can be applied to both freshwater and seawater ecotoxicological tests and the results subsequently interpreted. However, it is now known that there is a wide variability in the extent of this complexation. In this context, the removal of toxicity caused by the presence of Hg²⁺, Cd²⁺, Cu²⁺, Cr⁶⁺, Zn²⁺, Ni²⁺, Pb²⁺, Ag¹⁺ and Se²⁺, through metal complexation by EDTA and sodium thiosulfate, in relation to the performance of embryo-larval tests with the sea urchin Arbacia lixula was investigated. It was observed that EDTA was capable of removing the toxicity of Pb²⁺, Zn²⁺ and Cu²⁺ while sodium thiosulfate only reduced the toxicity of Ag¹⁺. Compared to the complexation observed in freshwater ecotoxicological tests, the complexing agents used in this study (EDTA and sodium thiosulfate) have a lower capacity to complex metals in the marine ecotoxicological test with A. lixula.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.     

Atrazine promotes biochemical changes and DNA damage in a Neotropical fish species

The effects of Atrazine, an herbicide used worldwide and considered as a potential contaminant in aquatic environments, were assessed on the Neotropical fish Prochilodus lineatus acutely (24 and 48 h) exposed to 2 or 10 μg L⁻¹ of atrazine by using a set of biochemical and genetic biomarkers. The following parameters were measured in the liver: activity of the biotransformation enzymes ethoxyresorufin-O-deethylase (EROD) and glutathione S transferase (GST), antioxidant enzymes superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione reductase (GR), content of reduced glutathione (GSH), generation of reactive oxygen species (ROS) and occurrence of lipid peroxidation (LPO); in brain and muscle the activity of acetylcholinesterase (AChE) and DNA damage (comet assay) on erythrocytes, gills and liver cells. A general decreasing trend on the biotransformation and antioxidant enzymes was observed in the liver of P. lineatus exposed to atrazine; except for GR, all the other antioxidant enzymes (SOD, CAT and GPx) and biotransformation enzymes (EROD and GST) showed inhibited activity. Changes in muscle or brain AChE were not detected. DNA damage was observed in the different cell types of fish exposed to the herbicide, and it was probably not from oxidative origin, since no increase in ROS generation and LPO was detected in the liver. These results show that atrazine behaves as enzyme inhibitor, impairing hepatic metabolism, and produces genotoxic damage to different cell types of P. lineatus.     

Bacterial assisted phytoremediation for enhanced degradation of highly sulfonated diazo reactive dye

Purpose

Phytoremediation is the exploitation of plants and their rhizospheric microorganisms for pollutants treatment like textile dyes, which are toxic, carcinogenic and mutagenic from the effluent. The purpose of this work was to explore a naturally found plant and bacterial synergism to achieve an enhanced degradation of Remazol Black B dye (RBB).

Methods

In vitro cultures of Zinnia angustifolia were obtained by seed culture method. Enzymatic analysis of the plant roots and Exiguobacterium aestuarii strain ZaK cells was performed before and after decolorization of RBB. Metabolites of RBB formed after its degradation were analyzed using UV?CVis spectroscopy, high-performance liquid chromatography (HPLC), Fourier transform infrared (FTIR) and gas chromatography?Cmass spectrometry (GC-MS). Phytotoxicity studies were performed.

Results

The consortium ZE was found to be more efficient than individual plant and bacteria. Z. angustifolia roots showed significant induction in the activities of lignin peroxidase, laccase, DCIP reductase and tyrosinase during dye decolorization. E. aestuarii showed significant induction in the activities of veratryl alcohol oxidase, azo reductase and DCIP reductase. Analysis of metabolites revealed differential metabolism of RBB by plant, bacteria and consortium ZE. E. aestuarii and Z. angustifolia led to the formation of 3,6-diamino-4-hydroxynaphthalene-2-sulfonic acid, (ethylsulfonyl)benzene, and 3,4,6-trihydroxynaphthalene-2-sulfonic acid and propane-1-sulfonic acid, respectively, whereas consortium ZE produced 4-hydroxynaphthalene-2-sulfonic acid, naphthalene-2-sulfonic acid and 4-(methylsulfonyl)phenol. The phytotoxicity study revealed the nontoxic nature of the metabolites formed after dye degradation.

Conclusion

Consortium ZE was found to be more efficient and faster in the degradation of RBB when compared to degradation by Z. angustifoila and E. aestuarii individually.     

Phytoremediation of textile effluent and mixture of structurally different dyes by Glandularia pulchella (Sweet) Tronc

Plants of Glandularia pulchella (Sweet) Tronc. performed decolorization of structurally different dyes to varying extent because of induction of different set of enzymes in response to specific dyes. Differential pattern of enzyme induction with respect to time was obtained for lignin peroxidase, veratryl alcohol oxidase, tyrosinase and dichlorophenolindophenol reductase during the decolorization of dye mixture, whose combined action resulted in greater and faster decolorization of dyes. HPLC, FTIR and High Performance Thin Layer Chromatography (HPTLC) analysis confirmed degradation of dyes from textile effluent and mixture. HPTLC demonstrated progressive decolorization of dye mixture along with preferential degradation of the dyes. G. pulchella showed reduction in American Dye Manufacturer's Institute from 405 to 21 and 418 to 22, in case of textile effluent and mixture of dyes respectively. The non-toxic nature of the metabolites of degraded textile dye effluent and mixture of dyes was revealed by phytotoxicity studies.     

Particles in swimming pool filters--does pH determine the DBP formation?

The formation was investigated for different groups of disinfection byproducts (DBPs) during chlorination of filter particles from swimming pools at different pH-values and the toxicity was estimated. Specifically, the formation of the DBP group trihalomethanes (THMs), which is regulated in many countries, and the non-regulated haloacetic acids (HAAs) and haloacetonitriles (HANs) were investigated at 6.0≤pH≤8.0, under controlled chlorination conditions. The investigated particles were collected from a hot tub with a drum micro filter. In two series of experiments with either constant initial active or initial free chlorine concentrations the particles were chlorinated at different pH-values in the relevant range for swimming pools. THM and HAA formations were reduced by decreasing pH while HAN formation increased with decreasing pH. Based on the organic content the relative DBP formation from the particles was higher than previously reported for body fluid analogue and filling water. The genotoxicity and cytotoxicity estimated from formation of DBPs from the treated particle suspension increased with decreasing pH. Among the quantified DBP groups the HANs were responsible for the majority of the toxicity from the measured DBPs.     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Residential runoff as a source of pyrethroid pesticides to urban creeks

Pyrethroid pesticides occur in urban creek sediments at concentrations acutely toxic to sensitive aquatic life. To better understand the source of these residues, runoff from residential neighborhoods around Sacramento, California was monitored over the course of a year. Pyrethroids were present in every sample. Bifenthrin, found at up to 73 ng/L in the water and 1211 ng/g on suspended sediment, was the pyrethroid of greatest toxicological concern, with cypermethrin and cyfluthrin of secondary concern. The bifenthrin could have originated either from use by consumers or professional pest controllers, though the seasonal pattern of discharge from the drain was more consistent with professional use as the dominant source. Stormwater runoff was more important than dry season irrigation runoff in transporting pyrethroids to urban creeks. A single intense storm was capable of discharging as much bifenthrin to an urban creek in 3 h as that discharged over 6 months of irrigation runoff.