土壤铜形态和生物有效性对施用生物质炭的响应

采用改进的Tessier方法对土壤Cu形态进行分级,研究了添加生物质炭对土壤重金属Cu形态、生物有效性和小麦生长及生理指标的影响。结果表明,石灰性土壤中Cu主要以碳酸盐结合态、氧化态和残渣态形式存在,三者占土壤Cu的90%以上。添加生物质炭后,土壤中的碳酸盐结合态铜、氧化态铜含量有所减少,但不显著;有机物结合态铜含量增加了131.25%,达到极显著水平,其中主要增加了紧有机结合态。添加生物质炭在培养一定时间后（30 d后）土壤有效态铜含量降低,120天时最大降低幅度达50.66%,添加生物质炭提高了冬小麦的根系重、茎秆干重、籽粒干重和灌浆期旗叶叶绿素含量,降低了根系、茎秆和籽粒的含铜量以及超氧化物歧化酶（SOD）活性,并随着生物质炭施用量的增加有显著性差异。综合看来,生物质炭对土壤铜污染具有钝化作用。     

Effect of plant growth on copper solubility and speciation in soil solution samples

The effect of plant growth on copper solubility and speciation was studied in a 10-week pot experiment. A copper-tolerant grass variety (Agrostis capillaris L. var. Parys Mountain) was grown in pots that contained either clean (copper-total approx. 30 mg kg(-1)) or copper contaminated soil (copper-total approx. 170 mg kg(-1)) at two pH levels (4.7 and 5.5). Also, similar pots without vegetation were included in the study. Due to the addition of NH(4)NO(3) fertilizer and subsequent nitrification of ammonia to nitrate, soil pH decreased from 4.7 to 3.5 and from 5.5 to 4, respectively. In the planted pots, soil pH recovered faster after depletion of NH(4)(+). This resulted in a decrease in the calcium solution concentrations and an increase in the dissolved organic carbon (DOC) concentrations in the planted pots. However, this was only observed in the clean soil; in the contaminated soil no difference in DOC levels between bare and planted pots was observed. Copper solubility in the contaminated soil was lower in the presence of plants; in the clean soil no differences were observed between the bare and planted pots. In the planted pots, copper activities in solution in both clean and contaminated soils were two orders of magnitude lower than in the bare pots. Copper activities in the non-planted contaminated soil reached potentially toxic levels ([Cu]+/-10(-5) to 10(-6) M) in contrast to the lower levels in the planted pots ([Cu]+/-10(-7) to 10(-10) M). Data and model results show that plant growth improves pH, DOC and calcium in solution to such an extent that both the total dissolved copper concentration and the free metal activity in soils can be reduced. This stresses the potential beneficial role of plants for the immobilization and detoxification of metals in contaminated soils.     

Evaluation of factors influencing root-induced changes of copper fractionation in rhizosphere of a calcareous soil

Major factors influencing the root-induced copper fractionation changes within the rhizosphere of maize, wheat, pea, and soybean seedlings were evaluated using a contaminated calcareous soil. The effects of acidification, alkalization, and introduction of root exudates were investigated by addition of acid, alkaline and root exudates from solution cultures, prior to incubation and copper fractionation. Raw and sterilized soils were compared for changes of copper fractionation in the rhizosphere using rhizoboxes with maize, wheat, pea and soybean seedlings. The results indicated that the general trend in considerable changes was similar among the plant species studied. The rhizosphere experienced a depletion of carbonate associated and organic bound copper along with an accumulation of exchangeable and Fe-Mn oxide bound copper. The resulting significant influence of root exudates on copper fractionation appears to have been produced through complexation rather than acidification or alkalization. The increase in exchangeable copper in rhizosphere was strengthened by microorganisms.     

餐厨垃圾与铬污染土壤混合堆肥中铬形态的转化

进行了不同比例铬污染土壤与餐厨垃圾混合堆肥实验,分析了堆肥过程铬形态的变化、浸出液毒性以及种子发芽指数.结果表明,堆肥实验后,堆肥物料中可交换态和碳酸盐结合态的铬含量逐渐减少,最多可分别减少82.6%和72.69%,有机结合态的铬含量明显增加,最大增幅为106.58%;堆肥物料浸出液铬的浓度低于国家危险废物鉴别标准,浸...     

Accumulation of phenanthrene and pyrene in rhizosphere soil

A study was conducted to determine PAH concentrations in the rhizosphere of plants grown in soil containing phenanthrene or pyrene. The rhizosphere of tall fescue and wheat grown in sterile soil contained 4-5-fold higher pyrene concentrations than unplanted soil. The rhizosphere of several plant species grown in non-sterile soil temporarily contained appreciably more phenanthrene or pyrene than unplanted soil, but those PAHs were degraded with time. The data suggest that plants accumulate such hydrophobic compounds in the rhizosphere after facilitating their transport toward the roots.     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

Characteristics and chemical speciation of waste copper slag

Environmental Science and Pollution Research - Waste copper slag contains abundant valuable metal element Fe, and residual elements such as Cu, As, Pb, Zn, and Mo. Simply stockpiling or landfilling...     

Changes in arsenic fractionation, bioaccessibility and speciation in organo-arsenical pesticide amended soils as a function of soil aging

Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1500 mg kg⁻¹ of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P < 0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.     

Accumulation, speciation and cellular localization of copper in Sesbania drummondii

Growth, accumulation and intracellular speciation and distribution of copper (Cu) in Sesbania drummondii was studied using scanning-electron microscopy (SEM), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The growth of seedlings was assessed in terms of biomass accumulation. The growth of the seedling was enhanced by 73.5% at a low Cu concentration (50 mg l⁻¹) compared to the control treatment. Additionally, seedling growth was inhibited by 18% at 300 mg l⁻¹ Cu with respect to the control. Copper concentration in roots and shoots was increased with increasing Cu concentration in the growth solution. The accumulation of Cu was found to be higher in roots than in the shoots. At a concentration of 300 mg l⁻¹ Cu, the roots accumulated 27,440 mg Cu kg⁻¹ dry weight (dw) while shoots accumulated 1282 mg Cu kg⁻¹ dw. Seedlings were assessed for photosynthetic activity by measuring chlorophyll a fluorescence parameters: F_v/F_m and F_v/F₀ values. Photosynthetic integrity was not affected by any of the Cu treatments. The X-ray absorption spectroscopic (XAS) studies showed that Cu was predominantly present as Cu(II) in Sesbania tissue. In addition, from the XAS studies it was shown that the Cu exists in a mixture of different coordination states consisting of Cu bound to sugars and small organic acids with some possible precipitated copper oxide. From the EXAFS studies, the coordination of Cu was determined to have four equatorial oxygen(nitrogen) ligands at 1.96 Å and two axial oxygen ligands at 2.31 Å. Scanning-electron microscopy studies revealed the distribution of Cu within the seedlings tissues, predominantly accumulated in the cortical and vascular (xylem) regions of root tissues. In the stem, most of the Cu was found within the xylem tissue. However, the deposition of Cu within the leaf tissues was in the parenchyma. The present study demonstrates the mechanisms employed by S. drummondii for Cu uptake and its biotransformation.     

Runoff rates,chemical speciation and bioavailability of copper released from naturally patinated copper

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.     

Bacterial stimulation of copper phytoaccumulation by bioaugmentation with rhizosphere bacteria

Copper contaminated areas pose environmental health risk to living organisms. Remediation processes are thus required for both crop production and industrial activities. This study employed bioaugmentation with copper resistant bacteria to improve phytoremediation of vineyard soils and copper mining waste contaminated with high copper concentrations. Oatmeal plant (Avena sativa L.) was used for copper phytoextraction. Three copper resistant bacterial isolates from oatmeal rhizosphere (Pseudomonas putida A1; Stenotrophomonas maltophilia A2 and Acinetobacter calcoaceticus A6) were used for the stimulation of copper phytoextraction. Two long-term copper contaminated vineyard soils (Mollisol and Inceptisol) and copper mining waste from Southern Brazil were evaluated. Oatmeal plants substantially extracted copper from vineyard soils and copper mining waste. As much as 1549 mg of Cu kg?1 dry mass was extracted from plants grown in Inceptisol soil. The vineyard Mollisol copper uptake (55 mg Cu kg?1 of dry mass) in the shoots was significantly improved upon inoculation of oatmeal plants with isolate A2 (128 mg of Cu kg?1 of shoot dry mass). Overall oatmeal plant biomass displayed higher potential of copper phytoextraction with inoculation of rhizosphere bacteria in vineyard soil to the extent that 404 and 327 g ha?1 of copper removal were respectively observed in vineyard Mollisol bioaugmented with isolate A2 (S. maltophilia) and isolate A6 (A. calcoaceticus). Results suggest potential application of bacterial stimulation of phytoaccumulation of copper for biological removal of copper from contaminated areas.     

Arsenic and chromium speciation in an urban contaminated soil

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)?2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil.     

Changes in photochemical and antioxidant enzyme activities in maize (Zea mays L.) leaves exposed to excess copper

Changes in photosynthetic and antioxidant activities in maize (Zea mays L.) leaves of cultivars 3223 and 31G98 exposed to excess copper (Cu) were investigated. Cu treatment reduced the shoot and root length of both cultivars. No significant difference of Cu accumulation in the roots of both cultivars was observed while the cultivar 3223 accumulated significantly higher Cu in leaves than 31G98. The observed decreases in effective quantum efficiency of PSII, ETR and qP indicate an over excitation of photochemical system in 3223 compared to 31G98. The leaf chlorophyll and carotenoid contents of both cultivars decreased with increasing Cu concentration. A far higher production of anthocyanins in 31G98 has been observed than that of 3223. At 1.5 mM Cu concentration, all antioxidant enzyme activities increased in leaves of the cultivar 31G98 while there were no significant changes in SOD and GR activities in 3223 compared to the control except increased APX and POD activities. The lower Cu accumulation in leaves and higher antioxidant enzyme activities in 31G98 suggested an enhanced tolerance capacity of this cultivar to protect the plant from oxidative damage.     

Residual inorganic soil nitrogen in grass and maize on sandy soil

Nitrogen (N) remaining as inorganic ('mineral') soil N at crop harvest (N(minH)) contributes to nitrate leaching. N(minH) data from 20 (grass) and 78 (maize) experiments were examined to identify main determinants of N(minH). N-rate (A) explained 51% (grass) and 34% (maize) of the variance in N(minH). Best models included in addition crop N-offtake (U), offtake in unfertilised plots (U(0)), and N(minH) in unfertilised plots (N(minH,0)) and then explained up to 75% of variance. At low N-rates where apparent N recovery rho keeps to its initial value rho(ini), N(minH) keeps to its base level N(minH,0). At N-rates that exceed the value A(crit) where rho drops below rho(ini), N(minH) rises above N(minH,0) by an amount proportional to (rho(ini)-rho)A. About 80% of (rho(ini)-rho)A was found as N(minH,) in grass as well as in maize. The fraction (1-rho(ini))A does not appear to contribute to N(minH) at low N-rates (A< or =A(crit)) or at high N-rates (A>A(crit)).     

Interactions between plant and rhizosphere microbial communities in a metalliferous soil

In the present work, the relationships between plant consortia, consisting of 1-4 metallicolous pseudometallophytes with different metal-tolerance strategies (Thlaspi caerulescens: hyperaccumulator; Jasione montana: accumulator; Rumex acetosa: indicator; Festuca rubra: excluder), and their rhizosphere microbial communities were studied in a mine soil polluted with high levels of Cd, Pb and Zn. Physiological response and phytoremediation potential of the studied pseudometallophytes were also investigated. The studied metallicolous populations are tolerant to metal pollution and offer potential for the development of phytoextraction and phytostabilization technologies. T. caerulescens appears very tolerant to metal stress and most suitable for metal phytoextraction; the other three species enhance soil functionality. Soil microbial properties had a stronger effect on plant biomass rather than the other way around (35.2% versus 14.9%). An ecological understanding of how contaminants, ecosystem functions and biological communities interact in the long-term is needed for proper management of these fragile metalliferous ecosystems.     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Toxicity of copper on rice growth and accumulation of copper in rice grain in copper contaminated soil

Pot soil experiments showed that copper (Cu) is highly toxic to rice. Rice grain yields decreased exponentially and significantly with the increase of soil Cu levels. Rice grain yield was reduced about 10% by soil Cu level of 100 mg kg(-1), about 50% by soil Cu level of 300-500 mg kg(-1) and about 90% by soil Cu concentration of 1,000 mg kg(-1). Root was more sensitive to soil Cu toxicity than other parts of rice plant at relatively lower soil Cu levels (less than 300-500 mg kg(-1)), but the growth of whole rice plant was severely inhibited at high soil Cu levels (300-500 mg kg(-1) or above). Cu concentrations in rice grain increased with soil Cu levels below 150-200 mg kg(-1), but decreased with soil Cu levels above 150-200 mg kg(-1), with peak Cu concentration at soil Cu level of 150-20 mg kg(-1). Cu was not distributed evenly in different parts of rice grain. Cu concentration in cortex (embryo) was more than 2-fold that in chaff and polished rice. More than 60% of the Cu in grain was accumulated in polished rice, about 24% in cortex (embryo), and about 12% in chaff. So, about 1/3 of the Cu in rice grain was eliminated after grain processing (chaff, cortex and embryo was removed).     

Ozone exposure of field-grown winter wheat affects soil mesofauna in the rhizosphere

A 2-year open-top chamber experiment with field-grown winter wheat (Triticum aestivum L. cv. Astron) was conducted to examine the effects of ozone on plant growth and selected groups of soil mesofauna in the rhizosphere. From May through June in each year, plants were exposed to two levels of O₃: non-filtered (NF) ambient air or NF+ 40 ppb O₃ (NF+). During O₃ exposure, soil sampling was performed at two dates according to different plant growth stages. O₃ exposure reduced above- and below-ground plant biomass in the first year, but had little effect in the second year. The individual density of enchytraeids, collembolans and soil mites decreased significantly in the rhizosphere of plants exposed to NF+ in both years. Differences were highest around anthesis, i.e. when plants are physiologically most active. The results suggest that elevated O₃ concentrations may influence the dynamic of decomposition processes and the turnover of nutrients.     

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.