The leachability of carbon-14-labelled 3,4-benzopyrene from coal ash into aqueous systems

The leachability of polycyclic aromatic hydrocarbons from coal ash into aqueous systems was studied. Carbon-14-labeled 3,4-Benzopyrene (BaP) was deposited on coal fly ash by adsorption from the liquid phase in quantities of about 10 μg/g ash. After a thermal treatment in air at 120 °C for 2 hours the desorption of BaP was measured using aqueous solutions of acetone and methanol as extractants and liquid scintillation counting as detection method. In all cases the ¹⁴C-recovery was incomplete. Using water as extractant, ¹⁴C-recoveries of about 1 % were found. In the presence of a non-ionic surface active agent (Tween 80) the ¹⁴C-recovery was enhanced significantly. For these reasons further experiments under realistic waste disposal conditions are necessary.     

Changes in primary productivity associated with liming and reacidification of an Adirondack lake

The addition of calcium carbonate to a clearwater acidic lake had a significant effect on phytoplankton abundance and on the biomass-specific rate of production. Chlorophyll concentrations and productivity: biomass ratios were strongly correlated with changes in lake acidity associated with liming and reacidification (r2=0.89 and 0.73, respectively). Summer mean chlorophyll increased by 0.9 mg m(-3) for each unit increase in lake pH, whereas productivity:biomass ratios decreased from > 2 to < 1 with an increase in pH from 5.5 to 7.0. Higher phytoplankton standing crops after liming were attributed to lower grazing rates following the decline of the dominant zooplankton taxa. A model relating biomass-specific productivity to incident light levels was found to be useful in interpreting treatment effects on productivity. Incident light and biomass (based on chlorophyll) accounted for 81% of the variability in productivity at the treated site. Comparisons of photosynthesis-irradiance curves indicated that the maximum photosynthetic capacity was higher following the watershed liming, compared to data collected after lake liming and during reacidification.     

单液滴微萃取-气相色谱/质谱法检测水中多环芳烃

采用单液滴微萃取-气相色谱/质谱(GC/MS)法建立了检测水中多环芳烃(PAHs)的方法,研究了萃取溶剂种类、萃取时间、搅拌速度对萃取效率的影响,确定了最佳单液滴微萃取条件,该法用于水中PAHs的检测,16种PAHs的线性范围为0.2～7.0μg/mL,相关系数≥0.9784,检出限为0.002～0.190μg/mL,相对标准偏差为7.1%～15.1%,加标回收率在81%～122%.     

Remediation of waters contaminated with pentachlorophenol

We describe a simple method of remediating waters contaminated with pentachlorophenol (PCP), which involves filtering the water through clean soil. The filtrate is contaminant free and no PCP can be extracted from the soil. If the soil it treated with dilute acid, the filtrate is still contaminant free but 28.7% of the PCP can be extracted from the contaminated soil. Irradiating the soil with microwave energy either destroys or binds the PCP to the soil irreversibly such that none can be extracted after long periods of time.     

Surface and ground waters characterization in Tuscany (Italy) by using algal bioassay and pesticide determinations: comparative evaluation of the results and hazard assessment of the pesticides impact on primary productivity

Algal bioassays and pesticide analysis were joined in Tuscany regional monitoring of surface and ground waters. Results were compared. Waters affected algal growth in any of the following ways: stimulation, inhibition, stimulation at low concentrations and inhibition at higher concentrations. Most of ground waters inhibited algal growth whereas only a little percentage were contaminated with pesticide. Most of surface waters stimulated algal growth and a higher percentage were contaminated with pesticides. In waters with inhibitory effect toxicological parameters (EC50, EC25, EC10 and NOEC) were measured and compared; EC25 values were very close to NOEC values. Hazard to aquatic primary productivity for each pesticide found during chemical monitoring was evaluated; for this aim the margin of safety (MOS) was calculated by using algal toxicity and the pesticide concentration measured.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Ozone alters carbon allocation in loblolly pine: assessment with carbon-11 labeling

Loblolly pine (Pinus taeda L.) seedlings were exposed to 0.120 micromol mol(-1) (ppm) ozone for 7 h per day, 5 days per week for 12 weeks. No visible damage resulted from this regime. A short-lived radioisotope of carbon ((11)C) was used to characterize changes in plant physiology caused by ozone, the first time this technique has been used for ozone exposure studies. In comparison to plants kept in charcoal-filtered air, pines exposed to ozone exhibited reductions in photosynthesis (16%), speed of phloem transport (11%), phloem photosynthate concentration (40%) and total carbon transport toward roots (45%). Photosynthate not transported to the roots appeared to accumulate in the stems. Primary branches of pines exposed to ozone were some 50-60% heavier than those of control pines. Ozone was thus shown to have a significant short-term impact on phloem transport processes that results in a shift in allocation of photosynthate favoring stems.     

Determination of benzotriazoles in dishwasher tabs from Germany and estimation of the discharge into German waters

A method was developed for the determination of benzotriazoles (BTs) in dishwasher tabs. BTs consist of 1H-benzotriazole and/or tolyltriazole, i.e., a technical mixture of the two isomers 4-methylbenzotriazole and 5-methylbenzotriazole (5-MBT). The method consisted of weighing of an aliquot of the tab, addition of the internal standard 5-MBT, precipitation of the soaps with CaCl₂ and KOH, derivatization of the filtrate with acetic acid anhydride in a two-phase system, and analysis of the organic toluene layer by gas chromatography with mass spectrometry in the selected ion monitoring mode. Eleven of 12 different dishwasher tabs from the German market were tested positive with BTs ranging from 2 to 66 mg/tab. Dishwashing experiments were performed to show that at least 99 % of the BT amount used in the dishwasher did not remain on the dishes but was released into the wastewater treatment system. The annual release of BTs into the water system was estimated to be ~80 tons. Since 70 % or less of the BTs can be degraded in wastewater treatment plants, at least 24 tons are annually released into rivers in Germany.     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Portal absorption of 14C after ingestion of spiked milk with 14C-phenanthrene, 14C-benzo[a]pyrene or 14C-TCDD in growing pigs

Polycyclic aromatic hydrocarbons (PAHs) and dioxins are lipophilic organic pollutants occurring widely in the terrestrial environment. In order to study the PAHs and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) transfer in the food chain, pigs have been fed with milk mixed either with 14C-phenanthrene, with 14C-benzo[a]pyrene or with 14C-TCDD. The analysis of portal and arterial blood radioactivity showed that both PAHs and TCDD were absorbed with a maximum concentration at 4-6 h after milk ingestion. Then, the blood radioactivity decreased to reach background levels 24 h after milk ingestion. Furthermore, the portal and arterial blood radioactivities were higher for phenanthrene (even if the injected load was the lowest) than these of benzo[a]pyrene or these of TCDD, in agreement with their lipophilicity and water solubility difference. Main 14C absorption occurred during the 1-3 h time period after ingestion for 14C-phenanthrene and during the 3-6 h time period for 14C-benzo[a]pyrene and for 14C-TCDD. 14C portal absorption rate was high for 14C-phenanthrene (95%), it was close to 33% for 14C-benzo[a]pyrene and very low for 14C-TCDD (9%). These results indicate that the three studied molecules have a quite different behaviour during digestion and absorption. Phenanthrene is greatly absorbed and its absorption occurs via the blood system, whereas benzo[a]pyrene and TCDD are partly and weakly absorbed respectively. However these two molecules are mainly absorbed via the portal vein.     

Determination of perchlorate in selected surface waters in the Great Lakes Basin by HPLC/MS/MS

Surface water samples were collected from 55 sites in the Great Lakes Basin and analyzed for the presence of perchlorate using HPLC/MS/MS with an isotopically enriched internal standard. Sites included areas impacted by heavy industry, urbanization, agriculture and atmospheric deposition. Perchlorate was detected at several of the sites at concentrations close to the method detection limit (0.2 microg/l). Despite these low concentrations, its presence was confirmed by sample concentration and determination of the isotopic ratio of perchlorate. The presence of perchlorate at two of the sites was related to a fireworks display which had occurred prior to sampling. The other detections of perchlorate were in rivers/creeks draining watersheds which had high density livestock and crop farming activity. We suspect the two are related. To our knowledge, these are the first reported concentrations of perchlorate in Canadian surface waters.     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Effect of Al(III) speciation on coagulation of highly turbid water

In Taiwan, the turbidity of raw water for fresh water treatments can sometimes reach as high as 40 000 NTU due to intensive rainfall, especially in typhoon seasons. In response, water works often apply large quantities of coagulants such as polyaluminium chloride (PACl). In this study, simulated and natural highly turbid water was coagulated with two PACls, a commercial product (PACl-1) and a laboratory product (PACl-E). The Al species distributions of PACl-1 and PACl-E under various pH conditions were determined, and the corresponding coagulation efficiency was evaluated. The PACl-E has a wider range of operational pH, while the efficiency of PACl-1 peaks at around neutral pH. For simulated water up to 5000 NTU, the PACl-E was superior to PACl-1 at low dosage and in the pH range studied. Similar results were discovered with natural water, except that when the turbidity was extremely high, the coagulation efficiency of PACl-E decreased significantly due to the presence of large amounts of organic matter. The coagulation of PACl-E was closely related to the content of polycationic aluminium (Al₁₃) while that of PACl-1 was dictated by the amount of Al_c. The sludge from PACl-E coagulation had better dewaterability when the optimum dosage was applied. The experimental results suggest that for natural water up to 5000 NTU, PACl containing high Al₁₃ species is recommended for coagulation. In cases when the water contains high organic matter, efficient coagulation depends upon enmeshment by amorphous aluminium hydroxide.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

Ecotoxicological assessment for receiving waters with the premetamorphic tadpoles acute assay

The toxicity of receiving waters was evaluated by means of the young tadpoles assays. The sentinel organism was Bufo arenarum, an indigenous anuran species. The assayed water samples were taken from a highly polluted urban watercourse (Reconquista River, Buenos Aires, Argentina), characterized by high concentration of nitrites, phosphates and heavy metals. The toxicity of water samples was assessed performing the pass-fail test and by means of the NOEC and LC(50); TUs (toxic units) were also calculated. The effect of the addition of a positive control (Cd) on the toxicity of the river water samples was also examined. Water samples of three sites, characterised by their different degree of pollution, were assayed. The lethal response had a clear cut correspondence with the water quality of the sample evaluated by means of physicochemical parameters. In most cases, the dilution of the samples resulted in a significant reduction of their toxicity to TU values compatible to those stated by the USEPA for industrial effluents. It was concluded that (a) the used Bufo arenarum bioassay was an adequate method for assessing the toxicity of natural polluted water samples and (b) the three considered endpoints showed no important differences after 48 or 96 h of exposure, therefore we concluded that it may not be necessary to extend the assay for a longer period than 48 h.     

Coagulation of highly turbid suspensions using magnesium hydroxide: effects of slow mixing conditions

Laboratory experiments were carried out to study the effects of slow mixing conditions on magnesium hydroxide floc size and strength and to determine the turbidity and total suspended solid (TSS) removal efficiencies during coagulation of highly turbid suspensions. A highly turbid kaolin clay suspension (1,213?±?36 nephelometric turbidity units (NTU)) was alkalized to pH 10.5 using a 5 M NaOH solution; liquid bittern (LB) equivalent to 536 mg/L of Mg²⁺ was added as a coagulant, and the suspension was then subjected to previously optimized fast mixing conditions of 100 rpm and 60 s. Slow mixing speed (20, 30, 40, and 50 rpm) and time (10, 20, and 30 min) were then varied, while the temperature was maintained at 20.7?±?1 °C. The standard practice for coagulation-flocculation jar test ASTM D2035-13 (2013) was followed in all experiments. Relative floc size was monitored using an optical measuring device, photometric dispersion analyzer (PDA 2000). Larger and more shear resistant flocs were obtained at 20 rpm for both 20- and 30-min slow mixing times; however, given the shorter duration for the former, the 20-min slow mixing time was considered to be more energy efficient. For slow mixing camp number (Gt) values in the range of 8,400–90,000, it was found that the mixing speed affected floc size and strength more than the time. Higher-turbidity removal efficiencies were achieved at 20 and 30 rpm, while TSS removal efficiency was higher for the 50-rpm slow mixing speed. Extended slow mixing time of 30 min yielded better turbidity and TSS removal efficiencies at the slower speeds.     

Influence of ozone pollution and climate variability on net primary productivity and carbon storage in China's grassland ecosystems from 1961 to 2000

Our simulations with the Dynamic Land Ecosystem Model (DLEM) indicate that the combined effect of ozone, climate, carbon dioxide and land use have caused China's grasslands to act as a weak carbon sink during 1961-2000. This combined effect on national grassland net primary productivity (NPP) and carbon storage was small, but changes in annual NPP and total carbon storage across China's grasslands showed substantial spatial variation, with the maximum total carbon uptake reduction of more than 400gm(-2) in some places of northeastern China. The grasslands in the central northeastern China were more sensitive and vulnerable to elevated ozone pollution than other regions. The combined effect excluding ozone could potentially lead to an increase of 14Tg C in annual NPP and 0.11Pg C in total carbon storage for the same time period. This implies that improvement in air quality could significantly increase productivity and carbon storage in China's grassland ecosystems.     

Photolysis of beta-blockers in environmental waters

Many drugs such as beta-blockers have been shown to occur in aquatic environments. Even if adequate ecotoxicity data are not available, it is of primary importance to get informations about their fate in environmental waters, particularly about their photofate in sewage treatment plant effluents (STP). The main difficulties when studying pharmaceutical photochemical behaviour in environmental waters, are linked to the very low environmentally relevant concentrations (ng L(-1) to microg L(-1)) which can generate problems in terms of analytical sensitivity. Moreover, the complexity of environmental matrices can modify micropollutants degradation kinetics. The photodegradation of beta-blockers has been compared at two concentration levels (10 microg L(-1) and 10 mg L(-1)) and in two different matrices (pure water and STP effluent). It has been shown that the concentration does not influence beta-blockers degradation pathways, thus allowing the identification of degradation compounds using the 10 mg L(-1) solutions. Although environmental waters speed up the degradation process, the same photoproducts were appeared in both matrices. Using LC-MS/MS, hydroxyl radical additions have been identified as an important degradation pathway for especially pindolol, propranolol and timolol, leading to several positional isomers, corresponding to mono-, di- or tri-hydroxylations. Kinetics of appearance/disappearance of these photoproducts have been studied in STP effluents.