The Life-Cycle of Chlorine, Part IV

Some cyclic organo-chlorines share key characteristics to a significant degree, notably volatility, solubility in lipids, environmental persistence, a tendency to bioaccumulation, and toxicity to animals. A subset of this group has been designated "persistent organic pollutants" (POPs). Because of their volatility, persistence, and tendency to bioaccumulate, POPs are found in remote locations, such as the Arctic, far from the locations where they were initially used or produced.
Except PCDDs (dioxins) and PCDFs (furans), all are, or were, originally produced for use as such , mainly as pesticides or herbicides. PCDDs and PCDFs have never been produced for their own sake; they are unwanted contaminants of chemical intermediates that were passed on and incorporated in final products, notably herbicides; they are also generated spontaneously in most combustion processes and chlorine bleaching of paper. Most POPs have been sharply restricted or banned outright in most of the industrialized countries, but not in less developed countries.
The qualities of persistence and bioaccumulation give special urgency to monitoring not only point source emissions and local concentrations, but also the mobile environmental reservoirs and exposure routes of these chemicals. To conduct adequate risk analyses, far more detailed data is needed on quantities produced and used, quantities and location of storage, mode of use, location of use, and period of use. Such data are not collected consistently by government or international agencies.     

Fly Larvae in Wastewater Discharges: A Potential Source of Food and Organochlorine Contaminants for some Southern California Fishes

A widely recognized pathway for uptake and accumulation of organic contaminants by demersal fishes is through consumption of infaunal organisms (i.e., those having direct contact with contaminated sediments). Recent studies indicate that demersal fishes near a large sewage outfall in southern California consume larvae of a terrestrial fly, Clogmia albipunctata, which are entrained with the treated effluent and discharged to the ocean. Fly larvae consumption represents a possible method for accumulation of organic contaminants that is unique to marine fishes with non-selective feeding habits that occur near the ocean outfall. An estimated 37–138kg (wet weight) of fly larvae are discharged daily during summer to the ocean via the Orange County Sanitation Districts (OCSD) wastewater outfall; winter discharges are expected to be lower due to lower production and temperature limitations of the fly life cycle. Fly larvae were present in the guts of ten demersal and pelagic fish species collected near the outfall between July 1993 and August 1998. The highest frequencies of fly larvae (up to 100%) occurred in the guts of white croaker, Genyonemus lineatus, and chub mackerel, Scomber japonicus. Because infauna are still abundant and diverse near the outfall, fly larvae consumption appears to represent a feeding preference instead of a response to lower prey abundances. Fly larvae tissues collected at the wastewater treatment plant contained sub-part-per-million levels of organochlorine compounds, including PCB and DDT. However, lipid-normalized organochlorine concentrations in fly larvae tissues were not appreciably higher than levels in infauna or zooplankton tissues. Although the study design provided only limited sample sizes for some sample types, this initial study suggests that fish consumption of fly larvae represents a mechanism for direct transfer of contaminants and may contribute to uptake and accumulation of lypophyllic organochlorines in fish near the outfall.     

The Importance of Nickel Phytoavailable Chemical Species Characterization in Soil for Phytoremediation Applicability

In this work Ni speciation in natural and spiked soils (with similar total concentration) was studied. Spiked soils were prepared by addition of NiSO₄.6H₂O to obtain concentration similar to the one in natural soils. In soils mobile species were determined with a simplified sequential extraction as follows: H₂O for water-soluble metal, KNO₃ for exchangeable species, DTPA for complexed/adsorbed species. Results show that in spiked soils the exchangeable and adsorbed Ni concentrations are considerably higher than in natural soils. A study of plant uptake was carried out in order to evaluate the relation between mobile species and phyto-availability. Alfalfa (Medicago sativa L.), even though it is not a hyperaccumulator, was selected for its tolerance to high metal concentrations in soil. Preliminary results show a very high correlation between Ni mobile species and Ni uptake by alfalfa. Significant differences were found between spiked and natural soils. In the latter, high levels of total Ni did not correspond to relevant uptake as in the case of spiked soil. Results stress the importance of evaluating preliminarly heavy metal speciation in soil before planning phytoremediation procedures.     

Tetracycline accumulates in Iberis sempervirens L. through apoplastic transport inducing oxidative stress and growth inhibition

Environmental antibiotic contamination is due mainly to improper and illegal disposal of these molecules that, yet pharmacologically active, are excreted by humans and animals. These compounds contaminate soil, water and plants. Many studies have reported the bioaccumulation of antibiotics in plants and their negative effects on photosynthesis, cell growth and oxidative balance. Therefore, the principal objective of this paper was the study of antibiotic accumulation sites in plants and its uptake modality. Iberis sempervirens L., grown in soil and in agar in the presence or absence of tetracycline, were used as a model system. Using confocal and transmission electron microscopy, we demonstrated that tetracycline was absorbed and propagated in plants through apoplastic transport and also accumulated in intercellular spaces. Tetracycline was rarely detected inside cells (in cytoplasm and mitochondria where, coherent to its pharmacological activity, it probably affected ribosomes), except in stomata. Moreover, we verified and clarified further the phytotoxic effects of tetracycline on plants. We observed that the antibiotic induced a large reduction in plant growth and development and inhibition of photosynthetic activity. As tetracycline may lead to oxidative stress in plants, plant cells tried to balance this disequilibrium by increasing the amount and activity of some endogenous enzyme antioxidant agents (superoxide dismutase 1 and catalase) and levels of antiradical secondary metabolites.     

Metals in Northern Forest Ecosystems: Role of Vegetation in Sequestration and Cycling,and Implications for Ecological Risk Assessment

Mass estimates of phytoaccumulated trace metal contaminants and transfers to soils are necessary to properly evaluate the impact of historic and continued anthropogenic metal deposition to northern forest ecosystems. An investigation of Cu, Ni, Pb, and Zn mass balances in plant communities subject to metal contamination from smelter emissions in Canada, found that accumulation of metals differed significantly among plant vegetation compartments (foliage, fine roots, bark, trunk, and branches). Analysis of plant community biological accumulation factors (BAFs), calculated using total soil metal and free soil metal ion (Me²⁺) found that free soil metal BAFs were more similar among locations than total soil metal BAFs, but that disparity still existed. Fine roots were found to dominate annual vegetation transfer of Cu, Ni, and Pb to soils, relative to foliage; fine root mortality played a smaller role than foliage for Zn plant-soil transfer. Plant-associated metal inputs were found to rival or exceed current estimates of atmospheric metal deposition, suggesting that potential benefits of future reductions in emissions to forests need to be evaluated within the context of phytocycling of metals already present.     

Studies on Cadmium Accumulation by Some Selected Floating Macrophytes

The results of investigation of the process of cadmium accumulation by floating plants of Eichhornia crassipes and Pistia stratiotes are discussed. The main specialty of this study is that it puts more emphasis on the mechanism of penetration of pollutant within the plant and its fate during accumulation act. As a result it was shown that at the first stage of cadmium uptake the sorption of the metal on the surface of the roots due to the presence of carboxylic groups takes place. At the root of the plant cadmium mainly localized in the cortex and rhizodermis, then the pollutant penetrates into the tissues of the stem according to its translocation factor. It has been also assumed that flavonoids perform an intermediate role in the accumulation of cadmium by the plant, taking part in the transport and combat an oxidative stress.     

Monitoring Copper Bioaccumulation in Cocoa from Copper-Based Pesticide–Treated Cocoa Farms Using Fuzzy Similarity Method

Cocoa production has been hindered by pests, leading to application of pesticides. These pesticide applications have raised health concerns. This study is therefore aimed at developing accumulation classifications for copper (Cu) in cocoa from plantations where Cu-based pesticides have been applied using fuzzy similarity method (FSM). Cocoa pods, seeds, leaves, and soil samples were collected from five different plantations from three states in Nigeria. The plant samples were digested using standard methods, whereas the Cu in soil samples was extracted with 1 M ammonium acetate. The products were analyzed for Cu using flame atomic absorption spectrophotometer. The Cu concentrations obtained were used to model the accumulation degree using FSM. The Cu concentrations were higher in the leaves than the seeds and the pods. The persistency of Cu was displayed by high concentrations (11.5–375 mg/kg) and enrichment factor in CRIN sites where this pesticide application has been stopped for over a decade. The leaves from Ondo sites had the highest Cu concentration, which indicates impact of recent applications. The FSM membership function and algorithm indicated that the plant parts had low degrees of accumulation for fresh leaves, pods, and seeds, the valued part applied in beverages, but for the dry leaves, the accumulation degree is high. It may be concluded that the applied Cu-based pesticide had more impact and accumulation on the leaves than the commercial valued seeds, but the Cu concentration in the seeds is above the recommended value.     

Integrated use of biomarkers and bioaccumulation data in Zebra mussel (Dreissena polymorpha) for site-specific quality assessment

One of the useful biological tools for environmental management is the measurement of biomarkers whose changes are related to the exposure to chemicals or environmental stress. Since these responses might vary with different contaminants or depending on the pollutant concentration reached in the organism, the support of bioaccumulation data is needed to prevent false conclusions. In this study, several persistent organic pollutants — 23 polychlorinated biphenyl (PCB) congeners, 11 polycyclic aromatic hydrocarbons (PAHs), six dichlorodiphenyltricholroethane (DDT) relatives, hexachlorobenzene (HCB), chlorpyrifos and its oxidized metabolite — and some herbicides (lindane and the isomers α, β, δ; terbutilazine; alachlor; metolachlor) were measured in the soft tissues of the freshwater mollusc Zebra mussel (Dreissena polymorpha) from 25 sampling sites in the Italian portions of the sub-alpine great lakes along with the measure of ethoxyresorufin dealkylation (EROD) and acetylcholinesterase (AChE) activity. The linkage between bioaccumulation and biomarker data allowed us to create site-specific environmental quality indexes towards man-made chemicals. This classification highlighted three different degrees of xenobiotic contamination of the Italian sub-alpine great lakes: a high water quality in Lake Lugano with negligible pollutant levels and no effects on enzyme activities, an homogeneous poor quality for Lakes Garda, Iseo and Como, and the presence of some xenobiotic point-sources in Lake Maggiore, whose ecological status could be jeopardized, also due to the heavy DDT contamination revealed since 1996.     

Effects of Copper Contamination on RumexK-1 Response

The effects of Cu contamination on RumexK-1 were studied using a pot trial. The results showed that the dry weight of leaves and roots did not change significantly under Cu stress when compared with CK (0 mg kg^?1 Cu). Additionally, there was no difference in the amounts of chlorophylla, chlorophyllb, chlorophyll (a+b), and the chlorophylla/b ratio between the CK and Cu treatments. The Cu accumulated in leaves and roots, particularly in the roots, with more Cu accumulating in the plants at higher Cu concentrations in the soil. The proline and soluble protein contents in the leaves were more sensitive to Cu contamination than in the roots. Finally, Cu contamination significantly inhibited the acid phosphatase, alkaline phosphatase, and peroxidase activities in the leaves. These results indicate that RumexK-1 is a plant that can accumulate Cu, exhibits some different metabolic mechanisms under Cu stress, and may be suitable for the phytoremediation of Cu contaminated soils.     

Enantiomer‐Specific In Vitro Biotransformation of Select Pharmaceuticals in Rainbow Trout (Oncorhynchus mykiss)

The occurrence of pharmaceuticals in the environment represents a challenge of emerging concern. Many pharmaceuticals are chiral compounds; however, few studies have examined the relative toxicity of pharmaceutical enantiomers to wildlife. Further, our understanding of stereospecific pharmacokinetics remains largely informed by research on humans and a few well‐studied laboratory test animals, and not by studies conducted with environmentally relevant species, including fish. The objective of this study was to investigate whether rainbow trout display stereospecific in vitro metabolism of three common chiral pharmaceuticals. Metabolism by trout liver S9 fractions was evaluated using a substrate depletion approach, which provides an estimate of intrinsic hepatic clearance (CL_{IN VITRO,INT}). No biotransformation was observed for rac‐, R‐, or S‐fluoxetine. Ibuprofen, including both enantiomers and the racemic mixture, appeared to undergo slow metabolism, but the resulting substrate depletion curves did not differ significantly from those of inactive controls. Contrary to relative clearance rates in humans, S(?)‐propranolol was more rapidly cleared than the R(+)‐ enantiomer. This work demonstrates that relative clearance rates and the effects of racemic mixtures in trout could not have been predicted based on human data. Additional research describing species differences and exploring tools for species extrapolation in biomedical and environmental studies is needed. Chirality 25:763–767, 2013, © 2013 Wiley Periodicals, Inc.