Revisions to the derivation of the Australian and New Zealand guidelines for toxicants in fresh and marine waters

The Australian and New Zealand Guidelines for Fresh and Marine Water Quality are a key document in the Australian National Water Quality Management Strategy. These guidelines released in 2000 are currently being reviewed and updated. The revision is being co-ordinated by the Australian Department of Sustainability, Environment, Water, Population and Communities, while technical matters are dealt with by a series of Working Groups. The revision will be evolutionary in nature reflecting the latest scientific developments and a range of stakeholder desires. Key changes will be: increasing the types and sources of data that can be used; working collaboratively with industry to permit the use of commercial-in-confidence data; increasing the minimum data requirements; including a measure of the uncertainty of the trigger value; improving the software used to calculate trigger values; increasing the rigour of site-specific trigger values; improving the method for assessing the reliability of the trigger values; and providing guidance of measures of toxicity and toxicological endpoints that may, in the near future, be appropriate for trigger value derivation. These changes will markedly improve the number and quality of the trigger values that can be derived and will increase end-users’ ability to understand and implement the guidelines in a scientifically rigorous manner.     

Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches

The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV–visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation–emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces.     

Spatial distribution and reduction of PCDD/PCDF Toxic Equivalents along three shallow lowland reservoirs

Reservoirs situated along a river continuum are ecosystems where rates of transfer of suspended matter and associated micropollutants are reduced due to sedimentation, accumulation, and biological and physical transformation processes. Among the micropollutants, PCDDs and PCDFs are substances that are highly toxic and carcinogenic for humans and animals. They are emitted and dispersed in the environment throughout the whole catchment area and may accumulate in aquatic and terrestrial food chains, creating a risk for human health. A wealth of data exists indicating the increase in the concentrations of pollutants along a river continuum. A comparative analysis of total, individual, and TEQ PCDD/PCDF concentrations in large lowland, shallow reservoirs located in different catchments (“I”—industrial/urban/agricultural, “U”—urban/agricultural, and “A”—agricultural/rural) showed decreases of the TEQ concentrations in bottom sediments along a gradient from the middle sections to the dam walls. Moreover, penta-, hexa-, and heptachlorinated CDD/CDF congeners were reduced from 28.8 up to 93.6 % in all three types of reservoirs. A further analysis of water samples from the inlets and outlets of the “A” reservoir confirmed this tendency.     

Probing the distribution and contamination levels of 10 trace metal/metalloids in soils near a Pb/Zn smelter in Middle China

The horizontal and vertical distribution patterns and contamination status of ten trace metal/metalloids (Ag, Bi, Co, Cr, Ge, In, Ni, Sb, Sn, Tl) in soils around one of the largest Chinese Pb–Zn smelter in Zhuzhou City, Central China, were revealed. Different soil samples were collected from 11 areas, including ten agricultural areas and one city park area, with a total of 83 surface soil samples and six soil cores obtained. Trace metal/metalloids were determined by inductively coupled plasma–mass spectrometry after digestion by an acid mixture of HF and HNO₃. The results showed that Ag, Bi, In, Sb, Sn, and Tl contents decreased both with the distance to the Pb–Zn smelter as well as the soil depth, hinting that these elements were mainly originated from the Pb–Zn smelting operations and were introduced into soils through atmospheric deposition. Soil Ge was influenced by the smelter at a less extent, while the distributions of Co, Cr, and Ni were roughly even among most sampling sites and soil depths, suggesting that they were primarily derived from natural sources. The contamination status, as revealed by the geo-accumulation index (I _geo), indicated that In and Ag were the most enriched elements, followed by Sb, Bi, and Sn. In general, Cr, Tl, Co, Ni, and Ge were of an uncontaminated status.     

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ^??) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ^?? aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH^?/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ^??-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.     

Pyrethroid pesticide effects on behavioral responses of aquatic isopods to danger cues

The present study sought to evaluate the behavioral responses of non-target organisms in order to determine whether phototactic responses of isopods to danger cues are altered as a function of exposure to the pyrethroid pesticides λ-cyhalothrin and bifenthrin. Experiments conducted on Gnorimosphaeroma oregonensis identified sublethal behavioral responses to pyrethroids, λ-cyhalothrin and bifenthrin at concentrations 0.15 ng/mL, 0.025 ng/mL, and 0.005 ng/mL. Experimental setup tested isopod phototactic responses across six treatments: control, pyrethroid, hemolymph, predator, hemolymph?+?pyrethroid, and predator?+?pyrethroid. Isopods exhibited no preference for phototactic responses in the control and pyrethroid treatments. When exposed to danger cues (hemolymph or predator), isopods exhibited significant negative phototaxis, as expected. When exposure to danger cues was combined with pyrethroids, isopods again exhibited no preference for phototactic response. Experiments indicate that pyrethroids diminish isopod’s negatively phototactic response to danger cues.     

Simazine biodegradation and community structures of ammonia-oxidizing microorganisms in bioaugmented soil: impact of ammonia and nitrate nitrogen sources

The objective of the present study was to investigate the impact of ammonia and nitrate nitrogen sources on simazine biodegradation by Arthrobacter sp. strain SD1 and the community structures of ammonia-oxidizing archaea (AOA) and bacteria (AOB) in non-agricultural soil. Soil microcosms with different treatments were constructed for herbicide biodegradation test. The relative abundance of the strain SD1 and the structures of AOA and AOB communities were assessed using quantitative PCR (q-PCR) and terminal restriction fragment length polymorphism (TRFLP), respectively. The co-existence of two inorganic nitrogen sources (ammonia and nitrate) had certain impact on simazine dissipation by the strain SD1. Bioaugmentation could induce a shift in the community structures of both AOA and AOB, but AOA were more responsive. Nitrogen application had significant impacts on AOA and AOB communities in bioaugmented soils. Moreover, in non-bioaugmented soil, the community structure of AOA, instead of AOB, could be quickly recovered after herbicide application. This study could add some new insights towards the impacts of nitrogen sources on s-triazine bioremediation and ammonia-oxidizing microorganisms in soil ecosystem.     

Occurrence,distribution, and multi-phase partitioning of triclocarban and triclosan in an urban river receiving wastewater treatment plants effluent in China

Occurrence, distribution, spatial and seasonal variations, and partitioning between aqueous phase and suspended particulate matters (SPM) of triclocarban (TCC) and triclosan (TCS) in Xiaoqing River, which receives wastewater treatment plant (WWTP) effluents, were studied. The distribution of the total TCC and TCS levels in surface water and sediments along the river were discussed. The highest TCC and TCS concentrations were both found near the discharge port of WWTPs, and the TCC and TCS levels decreased downstream of the WWTPs as a result of their distances from the source of WWTP discharges. The mean values of TCC and TCS in low-flow season were 1.62 and 1.80 times, respectively, as much as in high-flow season in surface water. The study on partitioning of TCC and TCS between aqueous phase and SPM shown the mean level of dissolved TCC accounted for about 10 % of the total level in surface water, whereas the TCS level was about 30 %. The TCC concentrations detected in the surface sediment samples (0 to 5 cm) ranged from 226 to 1,956 ng/g, with a mean value of 733 ng/g. The TCS levels were between 85 and 705 ng/g, with a mean value of 255 ng/g. The distribution and variations of TCC and TCS in sediments along the river were highly consistent with those in the water phase. The TCC and TCS levels in deep sediments (5 to 10 cm) were significantly lower than those in surface sediments. The mean TCC level in surface sediments was about 2.4 times as much as in deep sediments, and the TCS level in surface sediments was 3.1 times as much as in deep sediments.     

Biodegradation of methyl red by Bacillus sp. strain UN2: decolorization capacity,metabolites characterization,and enzyme analysis

Azo dyes are recalcitrant and refractory pollutants that constitute a significant menace to the environment. The present study is focused on exploring the capability of Bacillus sp. strain UN2 for application in methyl red (MR) degradation. Effects of physicochemical parameters (pH of medium, temperature, initial concentration of dye, and composition of the medium) were studied in detail. The suitable pH and temperature range for MR degradation by strain UN2 were respectively 7.0–9.0 and 30–40 °C, and the optimal pH value and temperature were respectively 8.0 and 35 °C. Mg²⁺ and Mn²⁺ (1 mM) were found to significantly accelerate the MR removal rate, while the enhancement by either Fe³⁺ or Fe²⁺ was slight. Under the optimal degradation conditions, strain UN2 exhibited greater than 98 % degradation of the toxic azo dye MR (100 ppm) within 30 min. Analysis of samples from decolorized culture flasks confirmed biodegradation of MR into two prime metabolites: N,N′dimethyl-p-phenyle-nediamine and 2-aminobenzoic acid. A study of the enzymes responsible for the biodegradation of MR, in the control and cells obtained during (10 min) and after (30 min) degradation, showed a significant increase in the activities of azoreductase, laccase, and NADH-DCIP reductase. Furthermore, a phytotoxicity analysis demonstrated that the germination inhibition was almost eliminated for both the plants Triticum aestivum and Sorghum bicolor by MR metabolites at 100 mg/L concentration, yet the germination inhibition of parent dye was significant. Consequently, the high efficiency of MR degradation enables this strain to be a potential candidate for bioremediation of wastewater containing MR.     

Effects of di-n-butyl phthalate on the physiology and ultrastructure of cucumber seedling roots

Agricultural pollution caused by the use of plastic sheetings has been documented to be a widespread problem in most of the major crop-planting regions of the world. In order to better understand the phytotoxic mechanisms induced by phthalic acid esters involved with this problem, Cucumber sativus L. cv Jinyan No. 4 were sown in pots to the three-leaf-stage in the presence of di-n-butyl phthalate (DBP; 0, 30, 50, 100, and 200 mg L^?1) for 1, 3, 5, or 7 days. Physiology, biochemistry, and ultrastructure of seedling roots were examined. The results indicated that activities of three antioxidant enzymes (superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD)) were stimulated at low-DBP treatments and decreased under higher levels (>100 mg L^?1) compared to the controls. On the other hand, SOD and POD provided a better defense against DBP-induced oxidative damage in the roots of cucumber seeding, compared to CAT. The productions of both malondialdehyde (MDA) and proline (Pro) were promoted under DBP stress. Visible impact on the cytoderm, mitochondrion, and vacuole was detected, possibly as a consequence of free radical generation. These results suggested that activation of the antioxidant system by DBP led to the formation of reactive oxygen species that resulted in cellular damage.