Toxicity of the weathered crude oil used at the Newfoundland offshore burn experiment (NOBE) and the resultant burn residue

The toxicity of the weathered crude oil Alberta sweet mixed blend (ASMB) used at the Newfoundland offshore burn experiment (NOBE) and the resultant burn residue, was investigated using the Environment Canada water-accommodated fraction (WAF) preparation method and exposure protocol. Rainbow trout (Oncorhynchus mykiss) were exposed to freshwater WAF prepared from weathered ASMB. Three-spine stickleback (Gasterosteus aculeatus), and the gametes of the white sea urchin (Lytechinus pictus) were exposed to saltwater WAF prepared from both weathered ASMB and burn residue. The fish tests were of 96 h duration, and the end-point was lethality. The urchin test was of 20 min duration, and the end-point was inhibition of fertilization. GC/MS headspace analysis of 28 analytes showed low levels of volatile hydrocarbons. The maximum measured concentration was 1.1 μg ml⁻¹ in 104 samples from all WAF concentrations in both seawater and freshwater at all exposure times (0, 24 and 72 h). All samples were found not to be toxic to all species tested.     

Correlation between physicochemical and ecotoxicological approaches to estimate landfill leachates toxicity

Leachates from municipal solid waste (MSW) landfills may contain a huge diversity of contaminants; these wastewaters should be considered as potentially hazardous complex mixtures, representing a potential environmental risk for surface and groundwater. Current MSW landfill wastes regulatory approaches deem exclusively on the physicochemical characterization and does not contemplate the ecotoxicological assessment of landfill leachates. However, the presence of highly toxic substances in consumer products requires reconsideration on the need of more specific ecotoxicological assessments. The main aim of this study was to evaluate the toxicity of different MSW landfill leachates using a battery of toxicity tests including acute toxicity tests with Daphnia magna and the anuran Xenopus laevis and the in vitro toxicity test with the fish cell line RTG-2. The additional objective was to study the possible correlation between physicochemical properties and the toxicity results obtained for untreated landfill leachates. The results showed that the proposed test battery was effective for the ecotoxicological characterization of MSW landfill leachates. A moderate to strong correlation between the measured physicochemical parameters and the calculated toxicity units was detected for all toxicity assays. Correlation factors of 0.85, 0.86 and 0.55 for Daphnia, Xenopus and RTG-2 tests, respectively, were found. The discriminant analysis showed that certain physicochemical parameters could be used for an initial categorization of the potential aquatic acute toxicity of leachates; this finding may facilitate leachates management as the physicochemical characterization is currently the most common or even only monitoring method employed in a large majority of landfills. Ammonia, alkalinity and chemical oxygen demand (COD), together with chloride, allowed a proper categorization of leachates toxicity for up to 75% of tested samples, with a small percentage of false negatives.     

Composition and Toxicity of Residual Bunker C Fuel Oil in Intertidal Sediments After 30 Years

In 1970, approximately 2000 m³ of Bunker C crude oil impacted 300 km of Nova Scotia’s coastline following the grounding of the tanker Arrow. Only 10% of the contaminated coast was subjected to cleanup, the remainder was left to cleanse naturally. To determine the long-term environmental impact of residual oil from this spill event, samples of sediment and interstitial water were recovered in 1993, 1997 and 2000 from a sheltered lagoon in Black Duck Cove. This heavily oiled site was intentionally left to recover on its own. Visual observations and chemical analysis confirmed that substantial quantities of the weathered cargo oil were still present within the sediments at this site. However, direct observations of benthic invertebrate abundance suggest that natural processes have reduced the impacts of the residual oil. To confirm this hypothesis, sediment and interstitial water samples from Black Duck Cove were assessed with a comprehensive set of biotests and chemical assays.Residual oil in the sediments had limited effect on hepatic CYP1A protein levels and mixed function oxygenase (MFO) induction in winter flounder (Pleuronectes americanus). No toxicity was detected with the Microtox solid phase test (Vibrio fischeri). Significant sediment toxicity was detected by the amphipod survival test (Eohaustorius estuarius) in four out of the eight contaminated sediments. Interstitial water samples were deemed non-toxic by the Microtox 100% test (Vibrio fischeri) and the echinoid fertilization test (Lytechinus pictus). Sediment elutriates were also found to be non-toxic in the grass shrimp embryo-larval toxicity (GSELTOX) test (Palaemonetes pugio).Recovery at this contaminated site is attributed to natural processes that mediated biodegradation and physical removal of oil from the sediments. In support of the latter mechanism, mineralization experiments showed that all test sediments had the capacity for hexadecane, octacosane and naphthalene degradation, while chemical analysis confirmed that the Bunker C oil from the Arrow had undergone substantial biodegradation.     

Ecotoxicological assessment and evaluation of a pine bark biosorbent treatment of five landfill leachates

When selecting a landfill leachate treatment method the contaminant composition of the leachate should be considered in order to obtain the most cost-effective treatment option. In this study the filter material pine bark was evaluated as a treatment for five landfill leachates originating from different cells of the same landfill in Sweden. The objective of the study was to determine the uptake, or release, of metals and dissolved organic carbon (DOC) during a leaching test using the pine bark filter material with the five different landfill leachates. Furthermore the change of toxicity after treatment was studied using a battery of aquatic bioassays assessing luminescent bacteria (Vibrio fischeri) acute toxicity (30-min Microtox®), immobility of the crustacean Daphnia magna, growth inhibition of the algae Pseudokirchneriella subcapitata and the aquatic plant Lemna minor; and genotoxicity with the bacterial Umu-C assay. The results from the toxicity tests and the chemical analysis were analyzed in a Principal Component Analysis and the toxicity of the samples before and after treatment was evaluated in a toxicity classification. The pine bark filter material reduced the concentrations of metal contaminants from the landfill leachates in the study, with some exceptions for Cu and Cd. The Zn uptake of the filter was high for heavily contaminated leachates (≥73%), although some desorption of zinc occurred in less contaminated waters. Some of the leachates may require further treatment due to discharge into a natural recipient in order to reduce the risk of possible biological effects. The difference in pH changes between the different leachates was probably due to variations in buffering capacity, affected by physicochemical properties of the leachate. The greatest desorption of phenol during filtration occurred in leachates with high conductivity or elevated levels of metals or salts. Generally, the toxicity classification of the leachates implies that although filter treatment with pine bark removes metal contaminants from the leachates effectively, it does not alter leachate toxicity noticeably. The leachates with the highest conductivity, pH and metal concentrations are most strongly correlated with an increased toxic response in the score plots of both untreated and treated leachates. This is in line with the toxicity classification of the leachate samples. The results from this study highlight the importance of evaluating treatment efficiency from the perspective of potential recipient effects, rather than in terms of residual concentrations of individual contaminants when treating waters with a complex contamination matrix, such as landfill leachates.     

Morphology,Chemical Characterization and Sources of Microplastics in a Coastal City in the Equatorial Zone with Diverse Anthropogenic Activities (Fortaleza city,Brazil)

Journal of Polymers and the Environment - The aim of the present study was to perform morphological and chemical characterizations of microplastics (MPs) found in seawater samples from the coast of...     

Chemical changes in different types of coal ash during prolonged,large scale,contact with seawater

In this study, we followed the chemical changes occurring in coal ash exposed to prolonged (300 days), large scale, contact with running seawater. Four major components (Al, Ca, Mg, Fe) and seven minor and trace elements (Cd, Cr, Cu, Mn, Zn, Pb, Hg) were measured in four coal ash types: fly and bottom ash freshly obtained from coal-fired power plant, and old ash (crushed and blocks) recovered from the sea after 3-5 years contact with seawater. Changes occurred in the chemical composition of the coal ash along the experiment: Fe increased in fresh ash, Al increased in old ash and Ca increased in all ash types except old ash blocks. Cu and Hg decreased in fresh fly ash while Cr increased, Cd decreased in all ash types except bottom ash, and Mn decreased in bottom ash. Most of the changes occurred in the fresh fly ash, and not in the old ash, indicating equilibrium after prior exposure to seawater. In addition, more changes occurred in fresh fly ash than in bottom ash, emphasizing the differences between the two ash types. While the changes in the concentrations of the major elements may be an indication of the integrity of the ash matrix, the only elements of environmental significance released to the environment were Hg and Cd. However, calculated seawater concentrations were much lower than seawater quality criteria and therefore the coal ash was considered suitable for marine applications concerning seawater quality.     

Toxicological evaluation of the chemical oxidation methods for landfill stabilization

As the stabilization criteria for landfill sites, only chemical criteria for the leachate discharges from the landfill sites have been used in Japan and many other countries. Recently, chemical oxidation has been developed as a method for the early-stabilization of landfills. However, by-products that are difficult to detect by chemical analysis can be produced by this method. Therefore, toxicity tests are useful tools for detecting the changes of leachate quality after application of this method. The heat source in the A landfill was analyzed by organic position inquiry technology, and ozone-treated leachate was sprayed back to the heat source in the landfill. Toxicity changes of the leachate after the spray were monitored using Microtoxtrade mark, ToxScreen-II, and DaphTox tests. The hardly-degradable organic matter was efficiently removed and toxicities of the leachate in the heat source decreased after the application. These toxicity results were significantly related to chemical oxygen demand (COD) changes. Thus, it was concluded that the toxicity tests were effective for monitoring the leachate quality after applying the chemical oxidation method for landfill stabilization, and its incorporation to establish the criteria for early-stabilization of landfill sites needs to be considered.     

Color analysis of combustion ashes of seawater-soaked wood: estimation of salt concentration

The color of wood ash is normally white, but black color ash was observed when seawater-soaked wood was combusted. In order to check the conditions for generation of black ash, we examined both ashing temperatures from 500 to 800 °C and seawater salt densities for wood soaking. As seawater salt densities rose, the ash color got black at ashing temperatures of 500 and 700 °C. The colors of the ash were analyzed by a spectrophotometer, and color space L* a* b* was measured. The L* value and wood ash yield showed a negative correlation when the ashing temperature was at 600 °C. Salt concentration in wood (SC) was practicably estimated from the L* value (R ² = 0.51) by the approximation formula [SC (%) = 11.82e^?0.038L*]. By scanning electron microscope (SEM) observation, black ash of 600 °C was fully covered by translucent material. It was composed of Na, Mg and Cl by energy dispersive X-ray spectroscopy analysis, and seemed to be crystallized seawater salt. Washed black ash was also observed by SEM, translucent seawater salt was removed and the wood tissue was observed. Black ash was found to be carbonized wood tissue residue, and it was generated when seawater salt exists with a woody biomass.     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

Characterization of iron elution for seaweed bed restoration using a steelmaking slag and compost method

Coastal areas in Japan and other parts of the world have serious problems with barren grounds. A method has been developed that uses a mixture of steelmaking slag and compost including humic substances supplied in seawater, for restoring seaweed beds. The effects of this method have been previously confirmed in field tests. It was found that the mixture of steelmaking slag and compost was effective for extending the lifetime of iron elution as well as increasing iron concentrations in seawater. In this study, the effect of the mixing composts with steelmaking slag was evaluated additionally for increasing dissolved iron concentrations in seawater. The characteristics of iron elution were also studied using this method. In particular, the mechanism of Fe elution and dissolved Fe oxidation was examined in detail. The iron elution of actual seawaters was tested using three kinds of samples which involved steelmaking slag, compost, and a mixture of steelmaking slag and compost. These samples were used to understand the mechanism of Fe elution and oxidation in seawater. It was found that the mixture of steelmaking slag and compost was the most effective, which also confirmed the validity of the proposed Fe elution process in seawater.     

Toxicity Evaluation with the Microtox Test to Assess the Impact of In Situ Oiled Shoreline Treatment Options: Natural Attenuation and Sediment Relocation

Changes in the toxicity levels of beach sediment, nearshore water, and bottom sediment samples were monitored with the Microtox^® Test to evaluate the two in situ oil spill treatment options of natural attenuation (natural recovery--no treatment) and sediment relocation (surf washing). During a series of field trials, IF-30 fuel oil was intentionally sprayed onto the surface of three mixed sediment (pebble and sand) beaches on the island of Spitsbergen, Svalbard, Norway (78°56^′ N, 16°45^′ E). At a low wave-energy site (Site 1 with a 3-km wind fetch), where oil was stranded within the zone of normal wave action, residual oil concentrations and beach sediment toxicity levels were significantly reduced by both options in less than five days. At Site 3, a higher wave-energy site with a 40-km wind fetch, oil was intentionally stranded on the beach face in the upper intertidal/supratidal zones, above the level of normal wave activity. At this site under these experimental conditions, sediment relocation was effective in accelerating the removal of the oil from the sediments and reducing the Microtox^® Test toxicity response to background levels. In the untreated (natural attenuation) plot at this site, the fraction of residual oil remaining within the beach sediments after one year (70%) continued to generate a toxic response. Chemical and toxicological analyses of nearshore sediment and sediment-trap samples at both sites confirmed that oil and suspended mineral fines were effectively dispersed into the surrounding environment by the in situ treatments. In terms of secondary potential detrimental effects from the release of stranded oil from the beaches, the toxicity level (Microtox^® Test) of adjacent nearshore sediment samples did not exceed the Canadian regulatory limit for dredged spoils destined for ocean disposal.     

海水烟气脱硫系统排水水质试验研究

介绍了海水烟气脱硫技术在国内外的应用情况,探讨了海水烟气脱硫系统的基本原理及工艺流程,并以海水水质标准为参照通过试验方法研究了脱硫排水对海水本底浓度的影响。     

DISCRISET: A battery of tests for fast waste classification – Application of tests on waste extracts

The Hazardous Waste Directive (HWD, Council Directive 91/689/EC, 1991) provides a framework for classification of hazardous waste, based on 15 Hazard (H)-criteria. For complex wastes the HWD foresees the application of toxicity tests on the waste material itself to assess its toxic properties. However, these proposed test methods often involve mammalian testing, which is not acceptable from an ethical point of view, nor is it feasible economically. The DISCRISET project was initiated to investigate the use of alternative chemical and biological fast screening tests for waste hazard classification. In the first part of the project, different methods were reviewed and a testing strategy was proposed to minimize time and cost of analysis by a tiered approach. This includes as a first tier chemical analysis followed by a general acute toxicity screen as a second tier and as a third tier mechanistic toxicity tests to assess chronic toxicity (genotoxicity, hormone disturbance, teratogenic effects, immunologic activity). In this phase of the project, selected methods were applied to 16 different waste samples from various sources and industries. The first tier chemical tests are recommended for the full characterization of the leachate fraction (inorganics) but not for the organic fraction of samples. Here the chemical characterization is only useful if toxic content is known or suspected. As second tier the fast bacterial test Microtox is validated as a general toxicity screen for the organic fraction (worst case organic extract). Samples that are not classified in tier 1 or 2 are then further investigated in the third tier by the mechanistic toxicity tests and tested for their potential chronic toxicity: immune activity (TNF-α upregulation) is indicative for corrosive, irritating or sensitising effects (H4/H8/H15), reproductive effects (H10) are indicated by hormone disturbance and early life stage abnormalities in fish larvae when exposed to the extracts and mutagenicity and carcinogenicity (H7, H11) are indicated by SOS response induction and increased mutation frequency in the Ames test when exposed to the extracts. Results indicate that the combination of chemical tests and bioassays allows important hazardous properties to be addressed and the tiered approach ensures that the tests are performed quickly and economically. The suggested strategy provides a solid and ethical alternative to the methods described in the HWD and is a vast improvement on the current, arbitrary classification.     

Toxicity of char residues produced in the co-pyrolysis of different wastes

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.     

Effectiveness of a biosurfactant in removing weathered crude oil from subsurface beach material

The University of Alaska Fairbanks Environmental Technology Laboratory is conducting ongoing research into the effectiveness of a biosurfactant, PES-51®, in removing weathered crude oil from beach material. A field test was conducted from 1 to 7 July 1993 in Sleepy Bay on La Touche Island in Prince William Sound. The results of chemical analysis of the beach material before and after treatment show that diesel range petroleum hydrocarbons are completely removed to levels below the detection limit of 0.5 mg kg⁻¹. Semivolatile petroleum hydrocarbons were reduced an average of 70%. The microbial data collected indicate that no inhibition of microbial activity in sediments is caused by treatment. The numbers and activity of hydrocarbon-degrading organisms were enhanced immediately following treatment and for about a month afterwards. There was no evidence of dissolved hydrocarbons or increased microbiological activity in seawater samples, providing evidence that oil was not transported offshore during the treatment process.     

发光细菌法测定有机工业废水综合毒性

应用发光细菌法对啤酒、酿造、印染、化纤、造纸废水进行了生物毒性测定；根据水质毒性分级标准对水样毒性进行了评价。结果表明，不同行业废水的生物毒性与其TOC值之间不存在相关性，只有将二者相结合，才能正确反映废水的实际毒性大小。发光细菌法用于工业废水毒性评价具有快速、简便、灵敏和准确的优点。     

Validation of Microtox as a first screening tool for waste classification

The Waste Framework Directive (WFD; 2008/98/EG) describes how waste materials are to be classified as hazardous or not. For complex waste materials chemical analyses are often not conclusive and the WFD provides the possibility to assess the hazardous properties by testing on the waste materials directly. As a methodology WFD refers to the protocols described in the CLP regulation (regulation on Classification, Labeling and Packaging of chemicals) but the toxicity tests on mammals are not acceptable for waste materials. The DISCRISET project was initiated to investigate the suitability of alternative toxicity tests that are already in use in pharmaceutical applications, for the toxicological hazard assessment of complex waste materials. Results indicated that Microtox was a good candidate as a first screening test in a tiered approached hazard assessment. This is now further validated in the present study. The toxic responses measured in Microtox were compared to biological responses in other bioassays for both organic and inorganic fractions of the wastes. Both fractions contribute to the toxic load of waste samples. Results show that the Microtox test is indeed a good and practical screening tool for the organic fraction. A screening threshold (ST) of 5 geq/l as the EC₅₀ value in Microtox is proposed as this ST allows to recognize highly toxic samples in the screening test. The data presented here show that the Microtox toxicity response at this ST is not only predictive for acute toxicity in other organisms but also for sub lethal toxic effects of the organic fraction. This limit value has to be further validated. For the inorganic fraction no specific biotest can be recommended as a screening test, but the use of direct toxicity assessment is also preferable for this fraction as metal speciation is an important issue to define the toxic load of elutriate fractions. A battery of 3 tests (Microtox, Daphnia and Algae) for direct toxicity assessment of this fraction is recommended in literature, but including tests for mechanistic toxicity might be useful.     

Assessment of compost dosage in farmland through ecotoxicological tests

A research project was carried out to evaluate ecotoxicological effects of mature compost addition to agricultural soil, using a battery of ecotoxicological tests. The following species were selected: plant of Lepidium sativum, earthworm Eisenia foetida, aquatic crustacean Daphnia magna and bacteria Vibrio fischeri. The tests were classified as “direct tests” using solid compost samples and “indirect tests” using compost leaching test eluate. The direct bioassays were performed using compost added to artificial soil in concentrations ranging from 2.5 to 100 % (w/w); the indirect ones considered compost eluate, added to a standard solution in the same concentrations used in the direct tests. Both tests aimed at obtaining the ecotoxicological parameters (LC₅₀ and EC₅₀). These values were then utilized to implement the Species Sensitivity Distribution (SSD) analysis and extrapolate the Hazard Concentration (HC), a useful threshold to preserve the biodiversity of agricultural ecosystems. Results indicated an increase in compost toxicity with greater compost concentrations; in particular, for direct tests compost dosage below 10 % showed low toxicity, while for indirect ones the toxicity was higher. Furthermore, SSD analysis showed a Hazardous Concentration (HC₅) for direct bioassays of 3.5 % and for indirect of 14 %.     

An ecotoxic risk assessment of residue materials produced by the plasma pyrolysis/vitrification (PP/V) process

Plasma is the fourth state of matter, following the three states of solid, liquid and gas. Experience has amply demonstrated that solids exposed to the oxygen-deficient plasma flame are converted to liquid, and liquid exposed to the same flame is converted to gas. A low amount of vitrified solid residue material usually remains at the end of this process. Plasma pyrolysis/vitrification (PP/V) has been demonstrated as a safe, efficient, cost-effective technology for the treatment of wastes, including hazardous wastes. Besides the low amounts of gaseous byproducts that PP/V produces, the solid vitrified residue presents a low leachability of pollutants. Studies have been performed in many countries in order to assess the leachability of chemical substances. But from the results of identified studies, none has reported results on the ecotoxicological properties of the leachates. The aim of this study was to contribute to the assessment of ecotoxic risk of four different vitrified materials. Vitrified samples of contaminated soils, municipal solid wastes, and incinerator bottom ashes were submitted to the European leaching pre-standard test number prEN 12457-2. The leachates were analyzed for 22 chemical parameters. The biological characterization comprised the assessment of bioluminescence inhibition of Photobacterium phosphoreum bacterium, growth inhibition of Pseudokirchneriella subcapitata algae and the germination inhibition of Lactuca sativa vegetable. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Toxicity (CEMWT) and a Toxicity Classification System (TCS). The chemical and ecotoxicological results indicated a low leachability of pollutants and a low toxicity level of leachates. All samples studied were as below the TCS class 1 level (no significant toxicity observed) and as non-ecotoxic for CEMWT. Therefore, the environmental ecotoxic risk of the analyzed vitrified samples was determined to be very low.     

Land treatment and the toxicity response of soil contaminated with wood preserving waste

Soils contaminated with wood preserving wastes, including pentachlo-rophenol (PCP) and creosote, are treated at field-scale in an engineered prepared-bed system consisting of two one-acre land treatment units (LTUs). The concentration of selected indicator compounds of treatment performance included PCP, pyrene, and total carcinogenic polycyclic aromatic hydrocarbons (TCPAHs) was monitored in the soil by taking both composited soil samples at multiple points in time, and discrete soil samples at two points in time. The mean concentration of the indicator compounds and the 95-percent confidence interval (CI) of the composite and discrete samples agreed relatively well, and first-order degradation rate kinetics satisfactorily represented the mean chemical concentration loss of indicator compounds in the LTU. Toxicity of the soil, as measured by Microtox^TM assay of the soil extracts, indicated that toxicity reduction corresponded with indicator compound disappearance. No toxicity effects were observed with time in treated layers of soil (lifts) buried beneath highly contaminated lifts of newly applied soil. This indicated that vertical migration of soluble contaminants from such lifts had little effect on the microbial activity in the underlying treated soil.