Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine, South China

Heavy metal contamination of soils resulting from mining and smelting is causing major concern due to the potential risk involved. This study was designed to investigate the heavy metal (Cu, Zn, Pb and Cd) concentrations in soils and food crops and estimate the potential health risks of metals to humans via consumption of polluted food crops grown at four villages around the Dabaoshan mine, South China. The heavy metal concentrations in paddy and garden soils exceeded the maximum allowable concentrations for Chinese agricultural soil. The paddy soil at Fandong village was heavily contaminated with Cu (703 mg kg^− 1), Zn (1100 mg kg^− 1), Pb (386 mg kg^− 1) and Cd (5.5 mg kg^− 1). Rice tended to accumulated higher Cd and Pb concentration in grain parts. The concentrations of Cd, Pb and Zn in vegetables exceeded the maximum permissible concentration in China. Taro grown at the four sampled villages accumulated high concentrations of Zn, Pb and Cd. Bio-accumulation factors for heavy metals in different vegetables showed a trend in the order: Cd > Zn > Cu > Pb. Bio-accumulation factors of heavy metals were significantly higher for leafy than for non-leafy vegetable. The target hazard quotient (THQ) of rice at four sites varied from 0.66-0.89 for Cu, 0.48-0.60 for Zn, 1.43-1.99 for Pb, and 2.61-6.25 for Cd. Estimated daily intake (EDI) and THQs for Cd and Pb of rice and vegetables exceeded the FAO/WHO permissible limit. Heavy metal contamination of food crops grown around the mine posed a great health risk to the local population through consumption of rice and vegetables.     

Mercury contamination in the vicinity of a chlor-alkali plant and potential risks to local population

A mercury-cell chlor-alkali plant operated in Estarreja (North-western Portugal) for 50 years causing widespread environmental contamination. Although production by this process ceased in 2002, mercury contamination from the plant remains significant. The main objective of this study was to investigate mercury impact on the nearby environment and potential risks to local population. To assess the level of contamination soil samples were collected from agricultural fields in the vicinity of the plant, extending the study by taking samples of the predominant vegetation suitable for animal and human consumption, water samples, and fish species from a nearby coastal lagoon, to gain a preliminary insight into the potential for contamination of the terrestrial and aquatic food web. To determine population exposure to mercury, hair samples were collected from local residents. Total mercury concentration in the 0-15 cm layer of soil was found to be highly variable, ranging between 0.010 and 91 mg kg^− 1, although mercury contamination of soils was found to be restricted to a confined area. Lolium perenne roots contained between 0.0070 and 2.0 mg kg^− 1, and there is evidence that root systems uptake mercury from the soil. Levels of mercury in the aerial parts of plants ranged between 0.018 and 0.98 mg kg^− 1. It appears that plants with higher mercury concentration in soils and roots also display higher mercury concentration in leaves.Total mercury concentration in water samples ranged between 12 and 846 ng L^− 1, all samples presenting concentrations below the maximum level allowable for drinking water defined in the Portuguese law (1.0 μg L^− 1).Mercury levels in fish samples were below the maximum limit defined in the Portuguese law (0.5 mg kg^− 1), ranging from 0.0040 to 0.24 mg kg^− 1. Vegetables collected presented maximum mercury concentration of 0.17 mg kg^− 1. In general, food is not contaminated and should not be responsible for major human exposure to the metal.Mercury determined in human hair samples (0.090-4.2 mg kg^− 1; mean 1.5 mg kg^− 1) can be considered within normal limits, according to WHO guidelines suggesting that it is not affecting the local population. Despite being subject to decades of mercury emissions, nowadays this pollutant is only found in limited small areas and must not constitute a risk for human health, should these areas be restricted and monitored.Considering the present data, it appears that the population from Estarreja is currently not being affected by mercury levels that still remain in the environment.     

Nitrifier characteristics in submerged membrane bioreactors under different sludge retention times

Three submerged membrane bioreactors (MBRs) were operated continuously for 230 days by feeding with synthetic inorganic wastewater (NH₄⁺-N, 100 mg L⁻¹) under different solids retention times (SRTs. M_30d, 30 days; M_90d, 90 days; M_infinite, no sludge purge) to examine the influence of SRT on nitrification performance and microbial characteristics. All the reactors could oxidize NH₄⁺-N to NO₃⁻-N effectively without accumulation of NO₂⁻-N. M_30d with the shortest SRT showed significantly higher specific ammonium oxidizing rate (SAOR, 0.22 kg NH₄⁺-N kg⁻¹ MLSS day⁻¹) and specific nitrate forming rate (SNFR, 0.13 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹) than the other two MBRs (0.12-0.14 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹ and 0.042-0.068 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹, respectively). Short SRT led to low extracellular polymeric substances (EPS) concentration and long operating cycle. The nitrite oxidizing bacteria (NOB) ratios by both the fluorescence in situ hybridization (FISH) (3.6% for M_30d and 2.1-2.2% for M_90d and M_infinite) and MPN (1.4 × 10⁷ cells g⁻¹ MLSS for M_30d and 6.2 × 10⁵ and 2.7 × 10⁴ cells g⁻¹ MLSS for M_90d and M_infinite) analyses showed that M_30d favored the accumulation of NOB, which was in accordance with the SNFR result. However, the ammonia oxidizing bacteria (AOB) ratios (3.5%, 3.2% and 4.9% for M_30d, M_90d and M_infinite) were not in accordance with the SAOR result. PCR-DGGE, clone library and FISH results showed that the fast-growing Nitrosomonas and Nitrobacter sp. were the dominant AOB and NOB, respectively for M_30d, while considerable slow-growing Nitrosospira and Nitrospira sp. existed in M_infinite, which might be an important reason why M_infinite had a low SAOR and SNFR.     

Determination of 210Po in various foodstuffs and its annual effective dose to inhabitants of Qena City, Egypt

The concentration of ²¹⁰Po was determined in different foodstuffs of plant origin purchased from markets in Qena City, Upper Egypt. Measurement of ²¹⁰Po has been carried out using alpha spectrometry technique in different food categories such as vegetables, fruits, cereals beverages and herbs. The general range of ²¹⁰Po activity levels ranged widely from < 0.010-18.6 ± 0.910 mBq g^− 1, with minimum being in cereal samples and maximum being in beverage samples. Tea samples recorded highest activity concentrations of ²¹⁰Po with lowest value of 10 ± 0.54 mBq g⁻¹ for Crown tea and highest value of 18.6 ± 0.910 mBq g⁻¹ for El maabad tea. The daily intake of ²¹⁰Po from food consumption reveals that vegetables are the biggest contributors, while beverages are the lowest. The effective ingestion dose has been estimated for Qena City residents and it was found in the range 0.008-38.3 μSv y⁻¹.     

Treating landfill leachate using passive aeration trickling filters; effects of leachate characteristics and temperature on rates and process dynamics

Biological ammoniacal-nitrogen (NH₄⁺-N) and organic carbon (TOC) treatment was investigated in replicated mesoscale attached microbial film trickling filters, treating strong and weak strength landfill leachates in batch mode at temperatures of 3, 10, 15 and 30 °C. Comparing leachates, rates of NH₄⁺-N reduction (0.126-0.159 g m^− 2 d^− 1) were predominantly unaffected by leachate characteristics; there were significant differences in TOC rates (0.072-0.194 g m^− 2 d^− 1) but no trend relating to leachate strength. Rates of total oxidised nitrogen (TON) accumulation (0.012-0.144 g m^− 2 d^− 1) were slower for strong leachates. Comparing temperatures, treatment rates varied between 0.029-0.319 g NH₄⁺-N m^− 2 d^− 1 and 0.033-0.251 g C m^− 2 d^− 1 generally increasing with rising temperatures; rates at 3 °C were 9 and 13% of those at 30 °C for NH₄⁺-N and TOC respectively. For the weak leachates (NH₄⁺-N < 140 mg l^− 1) complete oxidation of NH₄⁺-N was achieved. For the strong leachates (NH₄⁺-N 883-1150 mg l^− 1) a biphasic treatment response resulted in NH₄⁺-N removal efficiencies of between 68 and 88% and for one leachate no direct transformation of NH₄⁺-N to TON in bulk leachate. The temporal decoupling of NH₄⁺-N oxidation and TON accumulation in this leachate could not be fully explained by denitrification, volatilisation or anammox, suggesting temporary storage of N within the treatment system. This study demonstrates that passive aeration trickling filters can treat well-buffered high NH₄⁺-N strength landfill leachates under a range of temperatures and that leachate strength has no effect on initial NH₄⁺-N treatment rates. Whether this approach is a practicable option depends on a range of site specific factors.     

Selenium concentrations of common weeds and agricultural crops grown in the seleniferous soils of northwestern India

The plants grown in seleniferous soils constitute a major source of toxic selenium levels in the food chain of animals and human beings. Greenhouse and field experiments were conducted to study selenium concentrations of weeds, forages and cereals grown on seleniferous soils located between 31.0417° to 31.2175° N and 76.1363° to 76.4147° E in northwestern India. Eleven winter season (November-April) weed plants were grown in the greenhouse in a soil treated with different levels of selenate-Se. Selenium concentrations of weed plants increased progressively with the levels of selenate-Se in soil. The highest Se concentration was recorded by Silene gallica (246 mg kg^− 1) and the lowest by Avena ludoviciana (47 mg kg^− 1) at 2.5 mg Se kg^− 1 soil. A.ludoviciana and Spergula arvensis proved highly tolerant to the presence of 1.25 and 2.5 mg selenate-Se kg^− 1 soil and the remaining weeds were sensitive to Se. Dry matter yield of Se-sensitive weed plants was 25 to 62% of the yield in the no-Se control at 1.25 mg selenate-Se kg^− 1 and 6 to 40% at 2.5 mg selenate-Se kg^− 1 soil. Other symptoms like change in leaf colour and size, burning of leaf tips and margins, and delayed flowering were also observed due to Se. Dry matter yield of Se-sensitive weed plants expressed as percentage of yield in the no-Se control at both the Se levels was inversely correlated with their Se content (r = − 0.731, p < 0.01, N = 17). Among the weed plants grown in seleniferous soils under field situations, Mentha longifolia accumulated the highest Se (365 mg kg^− 1) and Phalaris minor the lowest (34 mg kg^− 1). Among agricultural crops grown on a naturally contaminated soil in the greenhouse, Se concentrations were the highest for oilseed crops (19-29 mg kg^− 1), followed by legumes (6-13 mg kg^− 1) and cereals (2-18 mg kg^− 1). Helianthus annuus among the oilseed crops, A.ludoviciana among the winter season weeds, M.longifolia among the summer season (May-October) weeds and Cirsium arvense among the perennial weeds can be used for phytoremediation of seleniferous soils as these accumulate the highest amounts of Se.     

Removal of organics in constructed wetlands with horizontal sub-surface flow: a review of the field experience

Constructed wetlands with horizontal sub-surface flow (HF CWs) have successfully been used for treatment various types of wastewater for more than four decades. Most systems have been designed to treat municipal sewage but the use for wastewaters from agriculture, industry and landfill leachate in HF CWs is getting more attention nowadays. The paper summarizes the results from more than 400 HF CWs from 36 countries around the world. The survey revealed that the highest removal efficiencies for BOD₅ and COD were achieved in systems treating municipal wastewater while the lowest efficiency was recorded for landfill leachate. The survey also revealed that HF CWs are successfully used for both secondary and tertiary treatment. The highest average inflow concentrations of BOD₅ (652 mg l^− 1) and COD (1865 mg l^− 1) were recorded for industrial wastewaters followed by wastewaters from agriculture for BOD₅ (464 mg l^− 1) and landfill leachate for COD (933 mg l^− 1). Hydraulic loading data reveal that the highest loaded systems are those treating wastewaters from agriculture and tertiary municipal wastewaters (average hydraulic loading rate 24.3 cm d^− 1). On the other hand, landfill leachate systems in the survey were loaded with average only 2.7 cm d^− 1. For both BOD₅ and COD, the highest average loadings were recorded for agricultural wastewaters (541 and 1239 kg ha^− 1 d^− 1, respectively) followed by industrial wastewaters (365 and 1212 kg ha^− 1 d^− 1, respectively). The regression equations for BOD₅ and COD inflow/outflow concentrations yielded very loose relationships. Much stronger relationships were found for inflow/outflow loadings and especially for COD. The influence of vegetation on removal of organics in HF CWs is not unanimously agreed but most studies indicated the positive effect of macrophytes.     

Dry deposition of gaseous radioiodine and particulate radiocaesium onto leafy vegetables

Radionuclides released to the atmosphere during dry weather (e.g. after a nuclear accident) may contaminate vegetable foods and cause exposure to humans via the food chain. To obtain experimental data for an appropriate assessment of this exposure path, dry deposition of radionuclides to leafy vegetables was studied under homogeneous and controlled greenhouse conditions. Gaseous ¹³¹I-tracer in predominant elemental form and particulate ¹³⁴Cs-tracer at about 1 μm diameter were used to identify susceptible vegetable species with regard to contamination by these radionuclides. The persistence was examined by washing the harvested product with water. The vegetables tested were spinach (Spinacia oleracea), butterhead lettuce (Lactuca sativa var. capitata), endive (Cichorium endivia), leaf lettuce (Lactuca sativa var. crispa), curly kale (Brassica oleracea convar. acephala) and white cabbage (Brassica oleracea convar. capitata). The variation of radionuclides deposited onto each vegetable was evaluated statistically using the non-parametric Kruskal-Wallis Test and the U-test of Mann-Whitney. Significant differences in deposited ¹³¹I and ¹³⁴Cs activity concentration were found among the vegetable species.For ¹³¹I, the deposition velocity to spinach normalized to the biomass of the vegetation was 0.5-0.9 cm³ g^− 1 s^− 1 which was the highest among all species. The particulate ¹³⁴Cs deposition velocity of 0.09 cm³ g^− 1 s^− 1 was the highest for curly kale, which has rough and structured leaves. The lowest deposition velocity was onto white cabbage: 0.02 cm³ g^− 1 s^− 1 (iodine) and 0.003 cm³ g^− 1 s^− 1 (caesium). For all species, the gaseous iodine deposition was significantly higher compared to the particulate caesium deposition. The deposition depends on the sensitive parameters leaf area, stomatal aperture, and plant morphology. Decontamination by washing with water was very limited for iodine but up to a factor of two for caesium.     

DDT contamination from indoor residual spraying for malaria control

The insecticide DDT is still used in specific areas of South Africa for indoor residual spray (IRS) to control malaria vectors. Local residents could be exposed to residues of DDT through various pathways including indoor air, dust, soil, food and water. The aims of this study were to determine the levels of DDT contamination, as a result of IRS, in representative homesteads, and to evaluate the possible routes of human exposure. Two villages, exposed (DV) and reference (TV) were selected. Sampling was done two months after the IRS process was completed. Twelve homesteads were selected in DV and nine in TV. Human serum, indoor air, floor dust, outside soil, potable water, leafy vegetables, and chicken samples (muscle, fat and liver) were collected and analyzed for both the o,p′- and p,p′-isomers of DDT, DDD and DDE. DDT was detected in all the media analyzed indicating a combination of potential dietary and non-dietary pathways of uptake. DV had the most samples with detectable levels of DDT and its metabolites, and with the exception of chicken muscle samples, DV also had higher mean levels for all the components analyzed compared to TV. Seventy-nine percent of participants from DV had serum levels of DDT (mean ∑ DDT 7.3 µg g⁻¹ lipid). These residues constituted mainly of p,p′-DDD and p,p′-DDE. ∑ DDT levels were detected in all indoor air (mean ∑ DDT 3900.0 ng m^− 3) and floor dust (mean ∑ DDT 1200.0 µg m^− 2) samples. Levels were also detected in outside soil (mean ∑ DDT 25.0 µg kg^− 1) and potable water (mean ∑ DDT 2.0 µg L^− 1). Vegetable sample composition (mean ∑ DDT 43.0 µg kg^− 1) constituted mainly p,p′-DDT and p,p′-DDD. Chicken samples were highly contaminated with DDT (muscle mean ∑ DDT 700.0 µg kg^− 1, fat mean ∑ DDT 240,000.0 µg kg^− 1, liver mean ∑ DDT 1600.0 µg kg^− 1). The results of the current study raise concerns regarding the potential health effects in residents living in the immediate environment following DDT IRS.     

Characterization of polychlorinated dibenzo-p-dioxin/dibenzofuran emissions from joss paper burned in a furnace with air pollution control devices

Burning joss paper, a common practice in temples in some Asian countries, can release toxic pollutants. This study investigated polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) emissions and profiles from burning joss paper in a temple furnace connected to two wet scrubbers. The mean total PCDD/F content and corresponding toxic equivalent quantity (TEQ) in joss paper were 193 ng kg^− 1 and 0.645 ng I-TEQ kg^− 1, respectively, whereas those in bottom ash from burned joss paper were 18.5 ng kg^− 1 and 1.92 ng I-TEQ kg^− 1, respectively. The wet scrubbers decreased individual PCDD/F emissions by 26.7-71.0% and those of total PCDD/Fs and I-TEQ by 47.2% and 66.0%, respectively. The total PCDD/F TEQ emission factors before and after the wet scrubbers were 8.14 and 3.42 µg I-TEQ ton-feedstock^− 1, respectively. The estimated total PCDD/F and corresponding TEQ emissions were 5.29 g year^− 1 and 0.462 g I-TEQ year^− 1, respectively, in Taiwan. Burning joss paper in temple furnaces is a significant source of PCDD/F emissions.     

Characteritization of, and health risks from, polychlorinated dibenzo-p-dioxins/dibenzofurans from incense burned in a temple

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) may cause adverse health effects. However, PCDD/F emissions from burning incense in temples have rarely been addressed. This study investigates PCDD/F emissions from burning incense in a temple. The mean total PCDD/F concentrations were 72.4-82.2 pg Nm^− 3 at two indoor sites; their corresponding mean total PCDD/Fs I-TEQ concentrations (0.24-0.27 pg I-TEQ Nm^− 3) were ~ 11 times that at a background location. In air samples collected from burning incense, OCDFs accounted for approximately 90% of total PCDD/Fs at the two indoor sites and an outdoor site near the temple, while the major PCDD/Fs in incense ash were PCDDs. The total PCDD/F content and toxic equivalent value of incense ash were 617 pg g^− 1 and 1.55 pg I-TEQ g^− 1, respectively. At the three sites inside/outside the temple, the air and ash samples contained the same four primary PCDD/Fs-OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF. The Cl⁻ emission factor, which is related to the PCDD/F formation, from burning incense was 0.454 mg g^− 1. The resultant lifetime average daily dose and cancer risk for temple workers were 0.00964 pg I-TEQ day^− 1 kg^− 1 and 9.64 × 10^− 6, respectively, approximately 2 times that for residents near the temple (0.00489 pg I-TEQ day^− 1 kg^− 1 and 4.89 × 10^− 6, respectively). We suggest that the chlorine content in incense must be regulated, and the high risk of PCDD/F exposure from burning incense for temple workers and visitors should be of concern.     

Temporal analysis of net fluvial methylmercury loading in a dystrophic and a clear water lake

The concentration of methylmercury (MeHg) in aquatic ecosystems is the net result of the highly dynamic abiotic and biotic processes of mercury methylation and demethylation. In this study, we conduct an examination of the net fluvial loading of methylmercury (MeHg_Net = MeHg_Watershed − MeHg_{Lake outflow}) across a 3 year time frame in both a dystrophic lake and an oligotrophic lake. A significant portion of MeHg_Net variance in both lakes could be attributed to a seasonal pattern (11.4%, p = 0.009; oligotrophic, and 27.0%, p < 0.0001; dystrophic) which in both cases, was most correlated with air temperature. The dystrophic lake appeared to be a net source of methylmercury (MeHg_Net = − 1.9 ± 0.3 mg MeHg d^− 1) while the oligotrophic lake appeared to be a net sink (MeHg_Net = 0.4 ± 0.2 mg MeHg d^− 1), indicating that there was net methylation in the dystrophic lake and net demethylation in the oligotrophic lake. Higher MeHg loading to the lakes occurred during the summer and between seasons there was a difference in MeHg_Net of 1.1 ±0.3 mg MeHg d^− 1 and 3.1 ± 0.6 mg MeHg d^− 1. Seasonal patterns of MeHg_Net in the oligotrophic lake lagged behind the dystrophic lake by 39 days. The short term variation in MeHg_Net was dominated by precipitation (t = 2.73, p = 0.008; dystrophic, t = 2.53, p = 0.017; oligotrophic).     

Significance and interspecific variability of accumulated trace metal concentrations in Antarctic benthic polychaetes

Trace metals were analysed in polychaetes collected on Polarstern cruise ANT XXI/2 (2003/04) to the Weddell Sea. Pb concentrations were largely less than 1.3 mg kg⁻¹ DW in all samples analysed. Statistical results indicate that the accumulated Cd, Cu and Zn concentrations are related to the feeding guild to which the animals are belonging. Relatively low Cd and Cu concentrations are found in macrophagous carnivores and relatively high concentrations in microphagous detritus feeders. The relationship between Zn concentrations and the feeding guilds of polychaetes is reverse. Cd concentrations range from (median values and interquantile ranges in brackets) 2.6 (1.5-3.2) mg kg⁻¹ DW in the carnivorous Trypanosyllis gigantea to 133 (37-176) mg kg⁻¹ in the microphagous detritus feeder Lanicides bilobata; Cu concentrations from 16 (11-19) mg kg⁻¹ in the carnivorous Antarctinoe spicoides to 40 (23-68) mg kg⁻¹ in the microphagous detritus feeder Phyllocomus crocea and Zn from 89 (69-97) mg kg⁻¹ in the microphagous detritus feeder Isocirrus yungi to 396 (372-404) mg kg⁻¹ in the carnivorous Aglaophamus trissophyllus. Ni is ranging from 3.7 (1.8-6.0) mg kg⁻¹ in Polyeunoa laevis to 34 (20-41) mg kg⁻¹ in A. spicoides, but no significant differences are obvious regarding the feeding guilds. Since information on metals in Antarctic polychaetes is almost completely lacking, our results suggest further studies to clarify the role of feeding in the bioaccumulation of metals in this ecologically important taxonomic group.     

The isotopic record of atmospheric lead fall-out on an Icelandic salt marsh since AD 50

We report a record of atmospheric Pb deposition at a coastal site in western Iceland that spans the last two millennia. The elemental concentrations of Pb, Al, Li and Ti are determined using ICP-MS from a sediment monolith collected from a salt marsh. Multicollector (MC) ICP-MS analysis is used to obtain isotopic ratios of stable Pb. The Pb/Ti and Pb/Li ratios are used to separate natural Pb background concentrations from Pb derived from remote anthropogenic sources. The pollution record in western Iceland is subdued in comparison with Pb records from the European mainland, but the isotopic character, profile and timing of Pb deposition show good agreement with the atmospheric Pb fall-out reported from sites in Scandinavia and northwestern Europe. At the bottom of the sequence we isolate a low-level (0.1-0.4 mg kg^− 1) Pb enrichment signal dated to AD 50-150. The isotopic signature and timing of this signal suggest Roman metal working industries as the source. In the subsequent millennium there was no significant or very low (i.e. elemental concentrations < 0.01 mg kg^− 1) anthropogenic Pb deposition at the site up to, and including, the early Medieval period. Above a pumice layer, dated to AD 1226-1227, a small increase in Pb deposition is found. This trend is maintained until a more substantive and progressive increase is signalled during the late 1700s and early 1800s. This is followed by a substantial enrichment signal in the sediments (> 3.0 mg kg^− 1) that is interpreted as derived from industrial coal burning and metal working during the 19th and 20th centuries in northern Europe. During the late 20th century, significant fall-out from European fuel additives reached Iceland.     

Impact of nickel and cobalt on biogas production and process stability during semi-continuous anaerobic fermentation of a model substrate for maize silage

The importance of nickel and cobalt on anaerobic degradation of a defined model substrate for maize was demonstrated. Five semi-continuous reactors were operated for 250 days at 35 °C and a well-defined trace metal solution was added to all reactors. Two reactors each were limited regarding the concentration of Ni²⁺ and Co²⁺, respectively, for certain time intervals. The required nickel concentration was depending on the organic loading rates (OLR) while, for example, above 2.6 g ODM L⁻¹ d⁻¹ nickel concentrations below 0.06 mg kg⁻¹ FM in the process significantly decreased biogas production by up to 25% compared to a control reactor containing 0.8 mg Ni²⁺ kg⁻¹ FM. Similarly, limitation of cobalt to 0.02 mg kg⁻¹ FM decreased biogas production by about 10%. Limitations of nickel as well as cobalt lead to process instability. However, after gradual addition of nickel till 0.6 mg and cobalt till 0.05 mg kg⁻¹ FM the OLR was again increased to 4.3 g ODM L⁻¹ d⁻¹ while process stability was recovered and a fast metabolisation of acetic and propionic acid was detected. An increase of nickel to 0.88 mg kg⁻¹ FM did not enhance biogas performance. Furthermore, the increase of cobalt from 0.05 mg kg⁻¹ FM up to 0.07 mg kg⁻¹ FM did not exhibit a change in anaerobic fermentation and biogas production.     

Remediation measures and displacement of pollutants in soils affected by the spill of a pyrite mine

The soils affected by the spill of a pyrite mine were analysed in 100 sampling points at three depths (0-10, 10-30, and 30-50 cm) in 1998 (after the tailings were removed), 1999 (after the cleaning of the highly contaminated areas), and 2004 (after the tilling of the upper 20-25 cm). The comparative study reveals that the removal of the tailings left a heterogeneous distribution pattern of the contaminants, with highly polluted spots alternating with less contaminated areas. The cleanup did not substantially lower the concentration in the highly polluted soils, and the spread of the pollutants increased the concentration in As and Pb in the uppermost 10 cm of 60% of the soils, while the Zn and Cd concentrations increased in only 30% of the soils. Given the high concentration of pollutants in the topsoil (especially As), the tilling of the upper 20-25 cm, despite reducing the average concentration of pollutants in the uppermost 10 cm, did not substantially lower the percentage of soils that exceeded the concentration of 40 mg As kg^− 1 dry soil and almost doubled the percentage of soils that surpassed this concentration between 10 and 30 cm. Meanwhile, the displacement of Zn and Cd within the soil supported the reduction in the percentage of soils that in the upper 10 cm exceeded the reference concentrations of these elements (900 mg Zn kg^− 1 dry soil and 2 mg Cd kg^− 1 dry soil), and the percentage of soils exceeding these concentrations between 10 and 50 cm in depth did not increase. Six years after the spill and at the end of all remediation measures, the intervention levels defined by the Environmental Agency of the Regional Government of Andalusia for natural parks were exceeded in the uppermost 10 cm in 35% of the soils.     

Copper clean-up procedure for ultrasonic extraction and analysis of pyrethroid and phenylpyrazole pesticides in sediments by gas chromatography-electron capture detection

A rapid ultrasonic extraction method coupled with a heated-copper clean-up procedure for removing interfering constituents was developed for analyzing pyrethroid and phenylpyrazole pesticides in sediments. Incubation of the 60 mL extract with 12 g copper granules at 60 °C for 2 h was determined to be the optimal conditions for removing the interfering constituents. Eleven pyrethroid and phenylpyrazole pesticides were spiked into sediment samples to determine the effectiveness of the ultrasonic extraction method. The average recoveries of pyrethroids and phenylpyrazoles in sediment at 4 °C storage on day 0, 1, 7, 14, and 21 ranged from 98.6 to 120.0%, 79.2 to 116.0%, 85.0 to 119.7%, 93.6 to 118.7%, and 92.1 to 118.2%, respectively, with all percent relative standard deviations less than 10% (most < 6%). This illustrated the stability of pyrethroids and phenylpyrazoles in sediment during sediment aging at 4 °C. Recoveries of the pesticides ranged from 98.6% to 120.0% for lowest fortification level (2-16 μg kg⁻¹), from 97.8% to 117.9% for middle fortification level (10-80 μg kg⁻¹), and from 94.3% to 118.1% for highest fortification level (20-160 μg kg⁻¹). Relative standard deviations of pesticide recoveries were usually less than 7%. Method detection limits of target pesticides ranged from 0.22 μg kg⁻¹ to 3.72 μg kg⁻¹. Furthermore, field sediment samples collected from four residential lakes during a three-month monitoring period were analyzed to evaluate the effectiveness of this method. Bifenthrin was detected in all of sediment samples (highest concentration 260.33 ± 41.71 μg kg⁻¹, lowest concentration 5.68 ± 0.38 μg kg⁻¹), and fipronil sulfone was detected at least once in sediment samples collected from three sites with concentrations ranging from 1.73 ± 0.53 to 7.53 ± 0.01 μg kg⁻¹.     

Assessment of chromium biostabilization in contaminated soils using standard leaching and sequential extraction techniques

The iron reducing microorganism Desulfuromonas palmitatis was evaluated as potential biostabilization agent for the remediation of chromate contaminated soils. D. palmitatis were used for the treatment of soil samples artificially contaminated with Cr(VI) at two levels, i.e. 200 and 500 mg kg^− 1. The efficiency of the treatment was evaluated by applying several standard extraction techniques on the soil samples before and after treatment, such as the EN12457 standard leaching test, the US EPA 3060A alkaline digestion method and the BCR sequential extraction procedure. The water soluble chromium as evaluated with the EN leaching test, was found to decrease after the biostabilization treatment from 13 to less than 0.5 mg kg^− 1 and from 120 to 5.6 mg kg^− 1 for the soil samples contaminated with 200 and 500 mg Cr(VI) per kg soil respectively. The BCR sequential extraction scheme, although not providing accurate estimates about the initial chromium speciation in contaminated soils, proved to be a useful tool for monitoring the relative changes in element partitioning, as a consequence of the stabilization treatment. After bioreduction, the percentage of chromium retained in the two least soluble BCR fractions, i.e. the “oxidizable” and “residual” fractions, increased from 54 and 73% to more than 96% in both soils.     

Releasing behavior of zinc in recirculated bioreactor landfill

The purpose of this research was to determine the releasing behavior of zinc in municipal solid waste (MSW) in landfill site with respect to refuse and leachate as an inseparable system. Two simulated bioreactor landfills, one with leachate recirculation and the other without, were operated in room temperature for 320 days. Results showed that the content of zinc in MSW could amount to 591.29 ± 31.33-632.14 ± 18.98 µg g ^− 1 dry weight ^− 1 (DW ^− 1). It exceeded the set standard for “Environmental quality standard for soil” (≤ 500 µg g ^− 1 DW ^− 1) and had high potential environmental risk. The releasing behavior of zinc in refuse mainly experienced speciation of solid-Zn, Zn²⁺, ZnHCO₃⁺, ZnCO₃, Zn(OH)⁺, Zn(OH)₂, Zn(NH₃)₄²⁺, ZnS, etc. Zinc in refuse showed behaviors of staggered migration and retention, which corresponded with the degradation process of refuse in bioreactor landfill. The Zn²⁺ concentration in leachate, which varied correspondingly with releasing behavior of zinc in refuse, were 0.75 mg L ^− 1 to 3.13 mg L ^− 1 and had no great difference in landfill with different operation modes (CL and RL). However, the amount of Zn²⁺ leached out from refuse, which accounted for 28.70 mg and 130.67 mg after 320 day's operation, respectively. More attention should be paid to the inseparable system including refuse and leachate together.     

A sustainable, carbon neutral methane oxidation by a partnership of methane oxidizing communities and microalgae

Effluents of anaerobic wastewater treatment plants are saturated with methane, an effective greenhouse gas. We propose a novel approach to treat such effluents using a coculture of methane oxidizing communities and microalgae, further indicated as methalgae, which would allow microbial methane oxidation with minimal CO₂ emissions. Coculturing a methane oxidizing community with microalgae in sequence batch reactors under continuous lightning yielded a factor of about 1.6 more biomass relative to the control without microalgae. Moreover, 55% less external oxygen supply was needed to maintain the methane oxidation, as oxygen was produced in situ by the microalgae. An overall methane oxidation rate of 171 ± 27 mg CH₄ L⁻¹ liquid phase d⁻¹ was accomplished in a semi-batch setup, while the excess CO₂ production was lower than 1 mg CO₂ L⁻¹ d⁻¹. Both nitrate and ammonium were feasible nitrogen sources for the methalgae. These results show that a coculture of microalgae and methane oxidizing communities can be used to oxidize dissolved methane under O₂-limiting conditions, which could lead to a novel treatment for dissolved methane in anaerobic effluents.