Toxicity identification in metal plating effluent: implications in establishing effluent discharge limits using bioassays in Korea

Because of complexity and diversity of toxicants in effluent, chemical analysis alone gives very limited information on identifying toxic chemicals to test organisms. Toxicity identification evaluation (TIE) techniques have been widely used to identify toxicants in various samples including industrial wastewater as well as natural waters. In response to new regulation for effluent discharge in Korea, which will be effective from 2011, a necessity of studies emerges that investigates toxicity levels in industrial effluents. This work was a preliminary study examining toxicity levels in effluent from one metal plating factory using Daphnia magna (48 h immobility) and identifying toxicity-causing substances. Toxicity tests showed variability on different sampling occasions and the results of TIE methods indicated that both organic compounds and metals contributed to the observed toxicity in metal plating effluent. Further studies are necessary to help reduce effluent toxicity especially from direct dischargers, who will have to comply with the new regulation.     

A comparative study of toxicity identification using Daphnia magna and Tigriopus japonicus: Implications of establishing effluent discharge limits in Korea

In Korea, the new permission criteria for industrial effluents based on Daphnia magna acute toxicity tests will be gradually implemented starting from 2011. Thus, in this study, toxicity assessment and identification using a marine species (Tigriopus japonicus) and the freshwater species (D. magna) was comparatively investigated. Effluent from an acid mine drainage treatment plant showed acute toxicity toward both organisms due to low pH, which was removed by neutralization of the effluent. Additionally, evaluation of the effluent of an electronics company revealed that Cu was attributable to the observed toxicity, and the effluent was more toxic toward T. japonicus than D. magna. Moreover, effluents from a metal plating factory were acutely toxic toward D. magna (6.50 TU), while they were not toxic against T. japonicus. Toxicity identification revealed that the high level of Cl⁻ (12,841 mg L⁻¹) was the cause of toxicity. Thus, the effluents had no effect on the marine species, T. japonicus. These findings suggest that a marine species rather than a freshwater species is more desirable for toxicity assessment of industrial effluent discharged into the saltwater, and thus should be considered in the legislation of toxicity-based discharge limits in Korea.     

Natural antifouling compounds produced by a novel fungus Aureobasidium pullulans HN isolated from marine biofilm

A fungus, Aureobasidium pullulans, was isolated from marine biofilm and identified. A bioassay-guided fractionation procedure was developed to isolate and purify antifouling compounds from A. pullulans HN. The procedure was: fermentation broth—aeration and addition of sodium thiosulfate–graduated pH and liquid–liquid extraction—SPE purification—GC–MS analysis. Firstly, the fermentation broth was tested for its toxicity. Then it was treated with aeration and addition of sodium thiosulfate, and its toxicity was almost not changed. Lastly, antifouling compounds were extracted at different pH, the extract had high toxicity at pH 2 but almost no toxicity at pH 10, which suggested the toxicants should be fatty acids. The EC₅₀ of the extract against Skeletonema costatum was 90.9 μg ml⁻¹, and its LC₅₀ against Balanus amphitrete larvae was 22.2 μg ml⁻¹. After purified by HLB SPE column, the EC₅₀ of the extract against S. costatum was 49.4 μg ml⁻¹. The myristic and palmitic acids were found as the main toxicants by GC–MS.     

A comparative study of toxicity identification using Daphnia magna and Tigriopus japonicus: implications of establishing effluent discharge limits in Korea

In Korea, the new permission criteria for industrial effluents based on Daphnia magna acute toxicity tests will be gradually implemented starting from 2011. Thus, in this study, toxicity assessment and identification using a marine species (Tigriopus japonicus) and the freshwater species (D. magna) was comparatively investigated. Effluent from an acid mine drainage treatment plant showed acute toxicity toward both organisms due to low pH, which was removed by neutralization of the effluent. Additionally, evaluation of the effluent of an electronics company revealed that Cu was attributable to the observed toxicity, and the effluent was more toxic toward T. japonicus than D. magna. Moreover, effluents from a metal plating factory were acutely toxic toward D. magna (6.50 TU), while they were not toxic against T. japonicus. Toxicity identification revealed that the high level of Cl- (12,841 mg L(-1)) was the cause of toxicity. Thus, the effluents had no effect on the marine species, T. japonicus. These findings suggest that a marine species rather than a freshwater species is more desirable for toxicity assessment of industrial effluent discharged into the saltwater, and thus should be considered in the legislation of toxicity-based discharge limits in Korea.     

Ecological risk assessment of trace metal accumulation in sediments of Veraval Harbor,Gujarat, Arabian Sea

In this study, different types of indices were used to assess the ecological risk of trace metal contamination in sediments on the basis of sediment quality guidelines at Veraval Fishery Harbor. Sediment samples were collected from three sectors in pre-, post-, and monsoon seasons in 2006. Trace metal concentrations were higher in the inner sector during post-monsoon, and it showed the highest statistical significance (p < 0.01) among the stations. Pollution load index was higher than unity, indicating alternation by effluent discharge from industries. Enrichment factor and geo-accumulation index showed that Cd, Pb, and Zn were enriched in the northern part of the harbor and Pb had accumulated in the harbor sediment. The ecological risk assessment index revealed that Ni, Zn, and Pb were higher than the effect range median values, indicating their potential toxicity to the aquatic environment in the Veraval Harbor. Hence, the harbor is dominated by anthropogenic activities rather than natural process.     

A Case Study on Identifying the Toxicant in Effluent Discharged from a Chemical Plant

Three phase procedures of toxicity identification evaluation (TIE) were conducted using Daphnia magna to identify the toxicant in effluent discharged from a chemical plant in Nanjing. Phase I toxicity characterization procedures suggested nonpolar organic compounds were responsible for the whole effluent toxicity. In phase II toxicity identification procedures, the effluent toxicity was recovered by C₁₈ solid-phase extraction and concentration steps. Gas chromatography–mass spectrometry (GC/MS) of the concentrate indicated that benzopyrone and phenol were present in the effluent at sufficient concentrations to cause the effluent toxicity. In phase III toxicity confirmation procedures, benzopyrone and phenol mixture tests and mass balance determinations with toxic units (TU) confirmed these compounds were the key toxicants accounting for 44.6% and 32.9% of the whole effluent toxicity, respectively.     

An evaluation of the toxicity and bioaccumulation of thallium in the coastal marine environment using the macroalga,Ulva lactuca

Thallium(I) has been added to cultures of the marine macroalga, Ulva lactuca, for a period of 48 h and the accumulation of the metal and its effects on the photochemical efficiency of photosystem II (PS II) measured. Thallium elicited a measurable toxic response above concentrations of 10 μg L⁻¹ in both coastal seawater (salinity 33) and estuarine water (salinity 20). The accumulation of Tl was defined by a linear relationship with aqueous Tl and accumulation factors of about 900 mL g⁻¹ in both media. Thallium accumulated by U. lactuca that was resistant to an EDTA extraction and, by operational definition, internalised, exceeded 90% in both cases. Accumulation and toxicity of Tl in the presence of a ∼10⁵-fold excess of its biogeochemical analogue, potassium, suggests that Tl has a high intrinsic phytotoxicity and that its mode of action involves permeation of the cell membrane as Tl⁺ through NaCl–KCl co-transporter sites rather than (or in addition to) transport through K⁺ ion channels.     

Importance of reversible attachment in predicting E. coli transport in saturated aquifers from column experiments

Drinking water wells indiscriminatingly placed adjacent to fecal contaminated surface water represents a significant but difficult to quantify health risk. Here we seek to understand mechanisms that limit the contamination extent by scaling up bacterial transport results from the laboratory to the field in a well constrained setting. Three pulses of Escherichia coli originating during the early monsoon from a freshly excavated pond receiving latrine effluent in Bangladesh were monitored in 6 wells and modeled with a two-dimensional (2-D) flow and transport model conditioned with measured hydraulic heads. The modeling was performed assuming three different modes of interaction of E. coli with aquifer sands: (1) irreversible attachment only (best-fit k_i = 7.6 day⁻¹); (2) reversible attachment only (k_a = 10.5 and k_d = 0.2 day⁻¹); and (3) a combination of reversible and irreversible modes of attachment (k_a = 60, k_d = 7.6, k_i = 5.2 day⁻¹). Only the third approach adequately reproduced the observed temporal and spatial distribution of E. coli, including a 4-log₁₀ lateral removal distance of ∼9 m. In saturated column experiments, carried out using aquifer sand from the field site, a combination of reversible and irreversible attachment was also required to reproduce the observed breakthrough curves and E. coli retention profiles within the laboratory columns. Applying the laboratory-measured kinetic parameters to the 2-D calibrated flow model of the field site underestimates the observed 4-log₁₀ lateral removal distance by less than a factor of two. This is promising for predicting field scale transport from laboratory experiments.     

Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa

Metal pollutants in water poses great threats to living beings and hence requires to be monitored regularly to avoid loss of lives. Various analytical methods are available to monitor these pollutants in water and can be improved with time. Modelling of metal pollutants in any water system helps chemists, engineers and environmentalists to greatly understand the various chemical processes in such systems. Water samples were collected from waste water treatment plant and river from highlands close to its source all the way to the ocean as it passing through areas with high anthropogenic activities. Pre-concentration of pollutants in the samples was done through acid digestion and metal pollutants were analysed using inductively coupled plasma-optical emission spectra (ICP-OES) to determine the concentration levels. Metal concentrations ranged between 0.1356–0.4658 mg/L for Al; 0.0031–0.0050 mg/L for Co, 0.0019–0.0956 mg/L for Cr; 0.0028–0.3484 mg/L for Cu; 0.0489–0.3474 mg/L for Fe; 0.0033–0.0285 mg/L for Mn; 0.0056–0.0222 mg/L for Ni; 0.0265–0.4753 mg/L for Pb and 0.0052–0.5594 mg/L for Zn. Modelling work was performed using PHREEQC couple with Geochemist’s workbench (GWB) to determine speciation dynamics and bioavailability of these pollutants. Modelling thus adds value to analytical methods and hence a better complementary tool to laboratory-based experimental studies.     

Assessing fertilization success of the coral Montipora capitata under copper exposure: Does the night of spawning matter?

Metal pollution is a major threat in tropical areas due to increasing pressure from anthropogenic activities along coastlines. Unfortunately there are very few toxicological studies that assess the effects of metals on marine organisms in tropical areas. To help fill this gap, this study investigated how Cu alters the fertilization success of the coral Montipora capitata over several nights of spawning. Results indicate that gametes of M. capitata are sensitive to Cu pollution, with EC₅₀ after 3 h ranging from 16.6 to 31.7 μg l^?1. Moreover, the sensitivity of the gametes to Cu toxicity was influenced by the night of spawning during which fertilization experiments were performed. This result likely reflected changes in the quality of gamete over the spawning period.     

Long-term perspective on the relationship between phytoplankton and nutrient concentrations in a southeastern Australian estuary

Sixteen years (1997–2013) of physicochemical, nutrient and phytoplankton biomass (Chlorophyll-a (Chl-a)) data and a decade (2003-2013) of phytoplankton composition and abundance data were analyzed to assess how the algal community in a temperate southeastern Australian estuary has responded to decreased chronic point source nitrogen loading following effluent treatment upgrade works in 2003. Nitrogen concentrations were significantly lower (P < 0.05) following enhanced effluent treatment and Chl-a levels decreased (P < 0.05) during the warmer months. Temperature and nutrient concentrations significantly influenced temporal changes of Chl-a (explaining 55% of variability), while salinity, temperature, pH and nutrient concentrations influenced phytoplankton abundance and composition (25% explained). Harmful Algal Bloom (HAB) dynamics differed between sites likely influenced by physical attributes of the estuary. This study demonstrates that enhanced effluent treatment can significantly decrease chronic point source nitrogen loading and that Chl-a concentrations can be lowered during the warmer months when the risk of blooms and HABs is greatest.     

Sublethal effects of the antibiotic tylosin on estuarine benthic microalgal communities

Pharmaceuticals are common chemical contaminants in estuaries receiving effluent from wastewater and sewage treatment facilities. The purpose of this research was to examine benthic microalgal (BMA) community responses to sublethal exposures to tylosin, a common and environmentally persistent antibiotic. Bioassays, using concentrations of 0.011–218 μmol tylosin l⁻¹, were performed on intertidal muddy sediments from North Inlet Estuary, SC. Exposure to tylosin resulted in a reduction in total BMA biomass and primary productivity. Furthermore, exposure seemed to retard diatom growth while having a minimal effect on cyanobacteria biomass. Estuarine systems receiving chronic inputs of trace concentrations of tylosin, as well as other antibiotics, may experience significant reductions in BMA biomass and primary productivity. Given the well-documented role of BMA in the trophodynamics of estuaries, these impacts will likely be manifested in higher trophic levels with possible impairments of the structure and function of these sensitive systems.     

Characteristics and role of groundwater dissolved organic matter on arsenic mobilization and poisoning in Bangladesh

The fluorescence and molecular weight characteristics of dissolved organic matter (DOM) in groundwater of Bangladesh were investigated to evaluate its multiple roles on arsenic (As) mobilization and poisoning. Fluorescence properties of DOM were measured in groundwater samples collected from two As contaminated areas of Bangladesh (Faridpur at the Ganges floodplain and Sonargaon at the Meghna floodplain) from different locations and depths. The three dimensional excitation–emission matrix (3DEEM) fluorescence spectra of groundwater samples showed two characteristic peaks around Ex/Em = 335–365 nm/435–480 nm for fulvic-like peaks and peak at around Ex/Em = 275–290 nm/310–335 nm for the protein-like materials. The similarity of fluorescence spectra of groundwater and surface water of both the study areas with high intensity of fluorescence and its strong correlation with DOC reflect the in situ generation of fluorescent DOM from sedimentary organic matter (SOM) and recent recharge of terrestrial labile organic carbon into shallow aquifer. High performance size-exclusion chromatography (HPSEC) analysis of DOM shows positive correlations between fluorescence intensities (FI) of small molecular fractions (0.65 kDa) and As concentrations, with the signatures of protein-like peaks of DOM in groundwater. This result provides new evidence that small molecular weight fraction of DOM in groundwater of Bangladesh can play an important role on As mobilization and toxicity. In addition, high concentration of fluorescence materials in DOM of As contaminated groundwater of Bangladesh may pose a threat to public health.     

Remediation studies of trace metals in natural and treated water using surface modified biopolymer nanofibers

In this study, remediation results of trace metals in natural water and treated water using three functionalized nanofiber mats of cellulose and chitosan are reported. The nanofiber materials, packed in mini-columns, were employed for the remediation of five toxic trace metals (Cd, Pb, Cu, Cr and Ni) from natural water samples. Trace metals in real water samples were undetectable as the concentrations were lower than the instrument’s detection limits of 0.27 × 10⁻³ (Cd) and 4.2 × 10⁻² (Pb) μg mL⁻¹, respectively. However, after percolation through the functionalised biosorbents in cartridges, detectability of the metal ions was enhanced. The starting volume of the natural water sample was 100 mL, which was passed through a column containing the nanofibers sorbent and the retained metals eluted with 5 mL of 2.0 M nitric acid. The eluate was analyzed for metals concentrations. An enrichment factor of 20 for the metals was realized as a result of the pre-concentration procedure applied to handle the determination of the metals at trace levels. The order of remediation of the studied metals using the nanofibers was as follows: chitosan/PAM-g-furan-2,5-dione < cellulose-g-furan-2,5-dione < cellulose-g-oxolane-2,5-dione. The modified biopolymer nanofibers were able to adsorb trace metals from the river water and treated water, thereby confirming their capability of water purification. These materials are proposed as useful tools and innovative approach for improving the quality of drinking for those consumers in small scale households.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40–350 ng Sn/g and 74–530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0–53 ng Sn/g dw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r² = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Content and distribution of trace metals in surface sediments from the northern Bering Sea,Chukchi Sea and adjacent Arctic areas

Concentrations of trace metals (Zn, Cr, Cu, V, Cd and Pb), total organic carbon (TOC), black carbon (BC) and their granulometry were examined in 25 surface sediment samples from the northern Bering Sea, Chukchi Sea and adjacent areas. Trace metal concentrations in the sediments varied from 21.06–168.21 mg kg⁻¹ for Zn, 8.91–46.94 mg kg⁻¹ for Cr, 2.69–49.39 mg kg⁻¹ for Cu, 32.46–185.54 mg kg⁻¹ for V, 0.09–0.92 mg kg⁻¹ for Cd, and 0.95–15.25 mg kg⁻¹ for Pb. The geoaccumulation index (I_geo) indicated that trace metal contamination (Zn and Cd) existed in some stations of the study area. The distribution of grain size plays an important role in influencing the distribution of trace metals (Zn, Cr, Cu, V, and Pb) in sediments from the Chukchi Sea and adjacent areas.     

Origin,toxicological and narcotic potential of sedimentary PAHs and remarkable even/odd n-alkane predominance in Bushehr Peninsula,the Persian Gulf

Surface sediments (n = 17) were collected from 6 sites located in the coasts of the Bushehr Peninsula. ∑₁₆PAH concentrations were in the range of 285.9–1288 ng g^? 1 dw and the sediments were moderately polluted. Py, Ph, B(a)A and Flu showed > 70% of the detected values in order of the mentioned rank. 4-ring PAHs were the dominant compounds and the molecular ratios presented the dominant pyrolytic source. The toxicity of PAHs for sediment dwelling life was averagely equivalent to occurrence of 0.08 ng g^? 1 of Dioxin in dw of the examined sediments. The evaluated narcotic potential (confidence level of 99%) was 0.027–3.04 and upper part of the Bushehr Peninsula, where the human population is more concentrated, showed more narcotic potential. ∑ n-alkane concentrations (n-C₁₅ ? n-C₃₂) were in the range of 3.10–35.6 μg g^? 1 dw. The dominant distribution of even carbon number n-alkanes was traced back to a possibly autochthonous source.     

Copper toxicity in the marine copepod Tigropus japonicus: Low variability and high reproducibility of repeated acute and life-cycle tests

The intertidal copeopod Tigriopus japonicus, which is abundant and widely distributed along the coasts of Western Pacific, has been suggested to be a good marine ecotoxicity testing organism. In this study, a series of experiments were conducted to investigate the reproducibility and variability of copper (Cu) sensitivity of T. japonicus so as to evaluate its potential to serve as an appropriate test species. To understand the seasonal variation of Cu sensitivity, individuals of T. japonicus were collected from the field in summer and winter, and subjected to standard 96 h acute (static renewal) toxicity tests. 96 h-LC50 values of T. japonicus collected from the two seasons were marginally different (p = 0.05), with an overall coefficient of variation (CV) of 33%. Most importantly, our results indicated that chronic Cu sensitivity of T. japonicus was highly reproducible. The CVs of intrinsic rates of increase in the population of the control and Cu treatment (10 μg Cu l⁻¹) groups were only 10–11% between 10 runs of a standardised complete life-cycle test. Moreover, different Cu(II) salts generally resulted in a similar 96 h-LC50 value while Cu(I) chloride was consistently slightly less toxic than Cu(II) salts. Given such a high reproducibility of toxic responses, it is advocated to use T. japonicus as a routine testing organism.     

Bioavailability of heavy metals in water and sediments from a typical Mediterranean Bay (Málaga Bay,Region of Andalucía,Southern Spain)

Concentrations of heavy metals were measured in sediment and water from Málaga Bay (South Spain). In the later twentieth century, cities such as Málaga, have suffered the impact of mass summer tourism. The ancient industrial activities, and the actual urbanization and coastal development, recreation and tourism, wastewaters treatment facilities, have been sources of marine pollution. In sediments, Ni was the most disturbing metal because Ni concentrations exceeded the effects range low (ERL), concentration at which toxicity could start to be observed in 85% of the samples analyzed. The metal bioavailability decreased in the order: Cd > Ni > Pb > Cu > Cr. In the sea water samples, Cd and Pb were the most disturbing metals because they exceeded the continuous criteria concentration (CCC) of US EPA in a 22.5% and 10.0% of the samples, respectively. Statistical analyses (ANOVA, PCA, CA) were performed.     

Lethal and estrogenic effects of 4-nonylphenol in the cockle Cerastoderma glaucum

The lethal and sublethal effects of the xenoestrogen 4-nonylphenol (NP) were evaluated in the cockle Cerastoderma glaucum. In a 96-h lethality test, bivalves were exposed to 0, 0+ acetone, 0.19, 0.38, 0.75, 1.5 and 3.0 mg NP/l. The 96-h LC₅₀ value was 0.3 mg NP/l. No mortality was observed at 0.1 mg NP/l. The potential estrogenicity of NP was studied in both sexually undifferentiated (resting phase) and differentiated (pre-spawning phase) cockles, exposed for 7 and 14 days to 0, 0+ acetone, 0.0125, 0.025, 0.05, and 0.1 mg NP/l. Vitellogenin (Vg)-like protein levels were determined in both haemolymph and digestive gland by the alkali-labile phosphate (ALP) assay. In the resting phase, exposure for 7 days to 0.1 mg NP/l resulted in significant increases in ALP in both haemolymph and digestive gland, compared with controls. A significant increase was also observed in digestive gland of animals exposed to 0.0125 mg NP/l-exposed animals. After 14 days of exposure, haemolymph ALP levels were significantly increased in exposed animals at all NP concentrations tested, whereas no difference was recorded in digestive gland. In the pre-spawning phase, exposure for 7 days to NP significantly increased ALP levels in haemolymph from males exposed at all NP concentrations tested, whereas no significant variations were found in haemolymph from females. NP (0.05 and 0.1 mg/l) was also shown to increase ALP concentrations significantly in digestive gland of males, but not in those of females. Likewise, after 14 days’ exposure, ALP levels significantly increased in haemolymph from males only at 0.1 mg NP/l. Conversely, NP caused significant increases in ALP levels in digestive gland from both males (at all NP concentrations tested) and females (at 0.025 and 0.1 mg NP/l). These results demonstrate that NP induces Vg synthesis in C. glaucum. Interestingly, males were more responsive to NP than females.