Accumulation of,and interactions between,calcium and heavy metals in wood and bark of Picea abies

Spreading of wood ashes from the pulp and paper industry will change the content and proportions of calcium (Ca), copper (Cu), cadmium (Cd), and zinc (Zn) in forest soils and thus also in the forest trees. The accumulation and distributions of, and interaction between, Ca and heavy metals in wood and bark of two‐year‐old Norway spruce (Picea abies [L.] Karst.) were investigated in this study. The treatment was carried out for 3 months in nutrient solutions, and there was a low or a high addition of Ca, Cd, Cu or Zn. The metal accumulation in, and distribution between, the bark, the wood formed during the treatment period (new wood), and the wood formed before the treatment period (old wood) was analyzed with AAS. The contents of the metals in the stems (i.e., bark, new wood, old wood) increased with elevated addition of the metal in question, also at the low addition of Ca, Cu, and Zn. Interactions between Ca and the heavy metals were found. Elevated Ca additions decreased the Cd content of the bark and the Zn content of the old wood, and tended to decrease the Cu content of the bark and the Cd content of the old wood. The Ca content decreased in both, wood and bark after Cu addition and the high Cd addition. Thus, even small changes in metal availability and proportions in forest soil, such as after spreading of wood ashes in the forest, will be reflected in the content of the metals in the wood and bark of forest trees.     

Retention of Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.     

Variations of trace element concentrations in red spruce tree rings

The potential of coniferous trees as biological indicators of heavy metal atmospheric pollution was investigated. In 31 municipalities of an industrialized region, samples of wood from the trunks of red spruce (Picea rubens) were taken to determine the spatial distribution of accumulated metals. Using the annual rings, these core samples were divided into 5-yr sections to determine temporal variations. The concentrations of Mg, Al, Ca, Mn, Fe, Cu, and Zn were measured by neutron activation analysis. All metals showed the highest concentrations in the most recent wood and the bark. For the wood older than 5 yr, Mn and Zn are stable with time, Mg and Ca decrease, while Al, Fe, and Cu appear to increase. A statistical analysis showed the municipalities with the highest variations in metal concentrations; it also revealed correlations in the fluctuations of several of the metals. As expected, trees in towns near metal refineries contain higher amounts of Mn, Fe, and Al. Large variations in metal concentrations, due to factors not totally understood, were observed. Thus, red spruce is not a sensitive bio-indicator of atmospheric metal pollution.     

Comparative effectiveness of selected adsorbant materials as potential amendments for the remediation of lead-, copper- and zinc-contaminated soil

Bonemeal, coir, compost, green waste compost, peat and wood bark all potentially could be used as amendments to remediate heavy metal contamination in soils. Their ability to sorb Pb, Cu and Zn was evaluated in the laboratory, using metal solutions ranging from 0 to 5 mmol/L as contaminants. The effects on sorption of metal concentration, background salt concentration and metal competition were evaluated. Single metal sorption by the six amendments was significantly different at metal concentrations of 1.5–5 mmol/L, with green waste compost, coir, compost and wood bark having the highest capacities to adsorb Pb, Cu and Zn. Langmuir sorption maxima were approximately 87 mg Pb/g (coir and green waste compost), 30 mg Cu/g (compost and green waste compost) and 13 mg Zn/g (compost and green waste compost) (equivalent to approx. 0.5 mmol/g of Pb and Cu, and 0.2 mmol/g Zn), all in a background solution of 0.001 M Ca(NO₃)₂. A higher background salt concentration and a combination of all three metals led to significant reduction in the amounts of Pb, Cu and Zn sorbed by all the amendments tested. Competing heavy metal cations in solution decreased Pb sorption to about 50–60% of that from a solution containing Pb alone; Cu sorption was reduced to about 30–40%; the effect of competition on Zn sorption was variable. Overall, in both single metal and competitive sorption, the order of strength of binding was Pb>Cu>>Zn.     

Soil metal immobilization and ryegrass uptake of lead, copper and zinc as affected by application of organic materials as soil amendments in a short-term greenhouse trial

Green waste compost, peat, coir and wood bark were applied to metal-contaminated mine waste at the rates of 1%, 10% and 20% on dry weight basis, and perennial ryegrass grown over a period of 6 weeks. Addition of amendments led to increased biomass yield in all soils when compared with the non-amended soil. EDTA extractable Pb, Cu and Zn was significantly reduced in amended soil, while leaf and root metal concentrations were also significantly reduced by the application of amendments, especially at applied rates of 10% and 20%. Coir, green waste compost and wood bark stood out as amendments which were consistent in reducing soil extractable and plant tissue Pb, Cu and Zn; while peat rates above 10% enhanced solubility of Cu and Zn because of a lowering of the soil pH.     

Evaluation of regional heavy metal deposition by multivariate analysis of element contents in pine tree barks

The airborne immission of heavy metals in the conservation area “Dübener Heide” nearby Bitterfeld was evaluated by biomonitoring studies with bark samples of 60-years-old scots pine (Pinus sylvestris L.). Nitric acid digestion and hydrochloric acid extraction of bark was followed by ICP-AES and ICP-MS analysis of the elements Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn. Fe and especially Cr were only partly soluble in hydrochloric acid. These elements deposited mostly as insoluble oxides, and their contents in the bark correlate significantly with Ca and S as elements of alkaline and acid deposition. Factor and cluster analysis of all element contents are used for the characterization and evaluation of heavy metal deposition types, which is shown to be a useful tool in forest monitoring control.     

长期化肥配施不同有机肥对土壤和玉米中重金属累积的影响

  【目的】  明确长期化肥配施有机肥对重金属元素在土壤和农作物籽粒、秸秆中积累的影响及其环境效应，为安全高效施肥提供科学依据。  【方法】  在北京市农林科学院新型肥料长期定位试验站进行了为期10年的田间试验，其种植模式为冬小麦–夏玉米轮作，试验处理为不施肥 (CK)、单施化肥 (NPK)、氮磷钾 + 鸡粪堆肥的有机肥料 (NPKJF)、氮磷钾 + 污泥堆肥的有机肥料 (NPKWN)、氮磷钾 + 垃圾堆肥的有机肥料 (NPKLJ) 和氮磷钾 + 秸秆粉碎还田 (NPKJG) 共6个处理，施肥处理依据等氮量施肥原则，每季作物施 N 180 kg/hm2、P₂O₅ 90.0 kg/hm2、K₂O 90.0 kg/hm2。在玉米收获后测定了玉米秸秆、籽粒和0—20 cm耕层土壤中重金属全量。  【结果】  添加污泥处理显著提高了土壤中Cd、Hg、As、Cu、Zn的含量，单因子污染指数分别比对照提高了45.10%、150.00%、104.00%、44.60%、65.80%。不同施肥处理对土壤中全量Cd、Cr、Hg、Cu、Zn存在一定的富集效果。各处理重金属单项污染指数在0.02～0.46，远小于1，综合污染指数为0.23～0.36，均小于0.7，试验区土壤重金属均为无污染等级。施用有机废弃物堆肥的处理玉米籽粒Cd、Cu、Zn含量比对照显著增加，各处理间Hg、As、Cr、Pb、Ni含量差异不显著，连续10年定位施肥后试验站土壤以及玉米籽粒中重金属含量均未超标。同一作物不同部位对重金属的富集能力不同，玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤Pb、Cu、Zn含量存在正相关性，玉米秸秆中Cd、Hg、Cr、Ni含量与土壤中Cd、Hg、Cr、Ni含量呈正相关或者显著负相关。  【结论】  在施氮总量不变的前提下，连续施用供试有机堆肥10年后，土壤重金属含量均未超标，土壤重金属单项污染指数在0.02～0.46，综合污染指数为0.23～0.36，无污染风险。只有污泥堆肥需要加强土壤Cd的监测。玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤相应重金属含量存在正相关性，秸秆中Cd、Pb、Hg、Zn与Cr、Ni含量与土壤中相应重金属含量呈正相关，而秸秆中Cr、Ni含量与土壤中相应重金属含量呈负相关。     

Effect of individual trees on the pH and the content of heavy metals in forest litters upon industrial contamination

The influence of individual spruce and birch trees on the distribution of heavy metals (Cu, Pb, Cd, and Zn) and hydrogen ions in the forest litter is considered in a territory subjected to long-term industrial pollution by emissions of the Ural copper smelter (town of Revda, Sverdlovsk oblast, southern taiga). In the background territory, the content of the elements regularly decreases from the tree trunks to the canopy gaps, whereas, in the contaminated territory, this relationship is either not traced at all (for the metal concentrations) or more weakly pronounced (for the metal reserves and pH values). The influence of trees on the spatial distribution of metals in the litter is specific for various elements and differs in coniferous and deciduous biotopes.     

Leaching of metals from the A-horizon of a spruce forest soil

The study quantifies the amount of metals (Na, K, Mg, Ca, Al, Fe, Mn, Ni, Cr, V, Cu, Zn, Cd, Pb) leached from the A-horizon of a podzolic spruce forest soil in southern Sweden during 2.5 yr, and offers statistical evidence of environmental conditions of importance to metal release. Considerable losses of Pb, Cr, Ni and V may occur from the A-horizon of forest soils under conditions favoring leaching of organic matter, Fe, and Al, i.e. during periods of comparably high soil temperature and moisture. Metals with a larger fraction present in exchangeable form (Na, Mg, Ca, Zn, Cd) are more susceptible to minor pH changes. An accelerated deposition or internal production of acidic matter therefore will reduce the retention times of these elements particularly.     

绿化植物废弃物对重金属迁移的影响

采用土柱模拟实验,比较研究了覆盖绿化植物废弃物与土壤之上和绿化植物废弃物与土壤混合处理对城市绿地土壤中重金属淋溶的影响。结果表明,Zn、Pb和Cd均在80天后淋溶完全,而Cu有所不同,在80天后又有增加的趋势,原因可能跟重金属与有机质的结合能力有关。此外,绿化植物废弃物与土壤相混合能抑制Cu、Zn、Pb和Cd向下淋溶,而绿化植物废弃物覆盖于土壤之上则有促进Cu、Zn、Pb和Cd淋溶的趋势,且不论是混合处理还是覆盖处理,20cm厚绿化植物废弃物的处理均比10cm厚绿化植物废弃物处理对Cu、Zn、Pb和Cd的促进或抑制作用大。研究还得知,Cu、Zn、Pb和Cd的迁移还与土壤pH有关,低pH土壤有利于重金属的淋溶。     

Efficient Purification of Heavy-Metal-Contaminated Water by Microalgae-Activated Pine Bark

Batch experiments were performed to study metal sorption by pine bark and algae-treated bark. The biosorption of copper (Cu), lead (Pb), zinc (Zn), cadmium (Cd), cobalt (Co), and nickel (Ni) in synthetic multimetal aqueous solutions was studied as a function of metal content in solution, and amount and size of bark particles used for sorption. Influence of water hardness (Ca²⁺ only was tested) on the metal sorption process was also evaluated. Metal uptake from solutions with high heavy metal content (i.e. 10× the limit for leachate from landfills) was found to be independent of Ca²⁺ concentration. At low metal content in solution (i.e. 1× the limit for leachate from landfills), uptake of Cu, Zn, Ni, and Cd decreased with increasing Ca²⁺ content in water. Microalgae-treated bark was found to increase the metal sorption efficiency. Air-drying of bark-entrapped algae was shown to be the best method for sorbent drying. In general, the green algae, Chlorella sp. and Pseudokirchneriella subcapitata showed the best results in metal uptake. Sorption of Co, Zn, Ni, and Cd from solution with high levels of both heavy metals and calcium increased by almost 50% with algae treatment of bark was applied. At low levels of metals and calcium content, 100% uptake of Cu and Pb in water was observed. Uptake of other metals from solution with low metal and Ca content was relatively high (50–60%). Low pH (pH 3.0) had no influence on metal sorption from solutions with high metal content. For solutions with low metal content a decrease of metal uptake by 10–15% was observed for all the metals but Pb. Thus, the treatment of bark with microalgae was successful and influenced positively the uptake capacity of the bark.     

农业废弃物中重金属含量特征及农用风险评估

为了解江西省主要农业废弃物中重金属污染状况和评估其再利用产物农用的安全性,在江西省内采集了水稻秸秆、蔬菜废弃物、猪粪和牛粪等样品,对样品中铬、镍、铜、锌、砷、镉、汞和铅重金属含量进行了测定与风险评估。结果表明,动物性废弃物中重金属含量和超标率明显高于植物性废弃物,其中猪粪属于重度污染,牛粪为轻度污染,植物性废弃物尚处于安全水平。若以江西省农业废弃物为原料制成有机肥,并长期施用于设施菜地,猪粪有机肥施用8.4、15.3和23.9 a后土壤中Cu、Cd和Zn将陆续超标,牛粪有机肥施用23.3 a后土壤中Cu将超标,水稻秸秆、蔬菜废弃物有机肥施用约29a后土壤中Cd将超标,故农业废弃物有机肥须严格控制原料中重金属含量,其农用的长期安全性有待加强监测。     

Radial distribution patterns of Cd and Zn in stems of Scots pine (Pinus sylvestris L.) trees analyzed 12 years after a contamination event

Radial distribution patterns of Cd and Zn in stems of Scots pine trees (Pius sylvestris L.) were investigated 12 years after a soil pollution event. The trees were growing on experimental plots near Krakow, southern Poland, which had been contaminated with heavy-metal-containing dust in 1980/81. The element distributions were examined for visible signals of the pollution event. Distributions of Cd and Zn in trees on contaminated plots showed elevated concentrations but were not uniform in shape. Only 2 of the 12 examined trees on plots with elevated Cd levels had highest Cd concentrations in xylem rings produced at the time of the pollution event. None of the sampled trees from the Zn plots had highest Zn concentrations in xylem rings which corresponded to the time of the pollution event. In the majority of sampled trees, concentrations of Cd and Zn decreased markedly in rings produced after the application of Cd and Zn dusts. In trees on contaminated plots concentrations of Cd and Zn were generally higher in sapwood than in heartwood. A sharp decline of both elements across the sapwood-heartwood boundary was observed. The distribution patterns of Cd and Zn are discussed with respect to endogenous physiological processes in stem wood. The element patterns observed in the wood of individual trees did not correspond to the known timing of pollution inputs to respective forest stands.     

不同树种下林下参土壤重金属含量差异分析

为解不同树种下林下参土壤中重金属含量的差异,以林下参护育中的胡桃楸、榆树、松树和杨树为研究对象,分析林下土壤中Al,Cd,Cr,Cu,Fe,Mn,Pb,V,Zn九种重金属含量。结果表明:不同树种下林下参土壤中重金属含量差别较大;重金属全量的变异系数以Cu最大,为0.33,而有效态含量的变异系数以Fe最大,达到了0.57;土壤中Cd的总量为0.390 mg/kg,大于国家土壤环境质量二级标准,值得引起注意;土壤中有效态Cd,Cu,Fe,Pb,V,Zn含量均以胡桃楸下为最高,有效态Al,Cr含量以松树下最高,杨树下有效态Cd,Cu,Fe的含量为各树种间最低;林下参重金属富集系数以Zn,Cu,Cr为最高,分别为0.445,0.473和0.279;林下参红皮病的发病指数以胡桃楸下最高而以杨树下最低,并与土壤中有效态铁含量呈显著正相关,与有效态锰含量呈显著负相关（p < 0.01）,相关系数分别为0.796和0.76。     

Influence of carbonate on the reaction of heavy metals in soils

The reaction of Cu, Zn and Cd with soils with carbonate contents ranging from 0 to 75 mg g⁻¹ was studied before and after removal of soil carbonates with acetate buffer at pH 5. Treatment with acetate buffer caused a strong decrease in metal retention by those soils containing carbonates, although if no carbonate was originally present, the treatment caused little effect or even an increase in the amounts sorbed. Before the treatment, adsorption of increasing amounts of Cu and Zn was accompanied by a continuous increase in Ca + Mg released, and those soils containing carbonate released Ca + Mg in excess of their exchangeable amounts, due to dissolution of carbonates and/or penetration of the heavy metal into the carbonate structure. It is suggested that Cu was preferentially retained by the treated soils through precipitation of Cu oxide, and by adsorption on the soil carbonates in the case of the original samples. Zn was removed from the solution by the original carbonate soils through formation of ZnCO₃. Treated soils were likely to retain Zn by cation exchange and/or adsorption. Adsorption was probably the main process involved in retention of Cd. In all cases pH was the master variable in controlling the extent and probably the nature of the reaction.     

Trace element distribution within the tree phytomass and forest floor of a tolerant hardwood stand,Algoma, Ontario

An examination of tree phytomass and trace metal concentrations (w/w) and pools in the tree stratum and forest floor of a sugar maple-yellow birch forest was carried out at Turkey Lakes Watershed, Algoma District, Ontario. Estimated aboveground tree phytomass (167, 500 kg ha^?1) was dominated by stemwood, branches > 2 cm, and stem bark. Highest trace metal concentrations were found in foliage (Cu, Fe, Mn, Ni) and stem bark (Cd, Pb, Zn). Concentrations of essential trace metals found in all sugar maple components followed the expected sequence of Mn>Fe>Zn>Cu. Lead and Ni concentations were always higher than those of Cd. Concentrations of essential elements in foliage and other components were comparable to those reported in the literature for other localities in North America. There was no indication that availability of essential trace elements (e.g., Cu) to vegetation had been increased as a result of increased atmospheric deposition. Lead, Ni and Cd levels in vegetation and forest floor were lower than those reported for similar forested areas of the northeastern United States.     

Die räumliche Variabilität von Schwermetall-Konzentrationen in Niederschlägen und Sickerwasser von Waldstandorten des Sollings

Local variability in the heavy metal concentrations of precipitation and seepage water from forest sites in the Solling Concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in precipitation and seepage water have been measured continuously with local replicates during a 6-months period at a beech and a spruce forest site. Variation coefficients of the avarage concentrations were, in most cases, well below 30 %, being mainly caused by local differences. Comparison of means showed a significant increase of heavy metal concentration in the canopy drip of beech (Mn, Fe, Pb) and spruce (Cr, Mn, Fe, Ni, Zn, Pb) compared to bulk precipitation measured in the open field. Concentration of Mn, Co, Ni, Zn and Cd in the seepage water is significantly higher under spruce compared to beech. These results point at higher filter efficiency of the spruce canopy, compared with beech, for air pollutants, but a smaller retention capacity of the soil under spruce for heavy metals.     

Additive effects of copper and zinc on cadmium toxicity on phosphatase activities and ATP content of soil as estimated by the ecological dose (ED50)

The ecological dose (ED₅₀) of Cd on alkaline and acid phosphatase activity and the ATP content of three contrasting forest soils was measured with or without Cu and Zn to assess the additive toxic effects of these two metals. Soils polluted with Cu and/or Zn were treated with increasing Cd concentrations to give the following metal combinations: Cd, Cd+Cu, Cd+Zn and Cd+Cu+Zn. Alkaline and acid phosphatase activities and ATP content of the three soils were analysed 4 h, 7 and 28 days after the metal additions. The ED₅₀ values were obtained by interpolating the enzyme activities or ATP data with a kinetic model and the goodness of fit was satisfactory.Generally, the ED₅₀ values of both acid and alkaline phosphatase activities for Cd were lower (higher toxicity) with than without Cu and Zn and the effect of Cu and Zn was particularly adverse when these two metals were both added to soils. The alkaline phosphatase was more sensitive in the acid and neutral soil whereas the acid phosphatase was more sensitive in the alkaline soil. Both phosphatase activities and the ATP content were more sensitive in the sandy than in the finer textured soils. The ATP content was less sensitive to the additive effects. Increasing toxicity was observed during the incubation.Analysis of 1 M NH₄NO₃-extractable Cd, Cu and Zn revealed that Cd competed with Zn for the adsorption sites but not with Cu. However, the lower ED₅₀ values for Cd of the two phosphatase activities and of the ATP content in the presence of heavy metal combinations could be not explained by the heavy metal solubility data. It is concluded that the ED₅₀ may be a sensitive tool for assessing additve toxic effects to soil biochemical parameters.     

Flüssebilanzen und aktuelle Änderungsraten der Schwermetall-Vorräte in Wald-Ökosystemen des Soiling

Flux balances and current rates of change of heavy metal stores in forest ecosystems of the Soiling The inventory of the heavy metals Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb is calculated for a beech and a spruce forest ecosystem in the Soiling mountains on the basis of measured concentrations in the vegetation and soil compartments and their dry mass per hectare. The inventory is compared with measured heavy metal fluxes coupled with precipitation above and below the canopy, with seepage water fluxes below the rooting zone (50 cm depth), with litterfall, and with the current increment to biomass. The ratios between heavy metal stores in the forest floor layers (table 3) and the annual flux with litterfall (table 4) show decreasing tendency for liberation of the elements by decomposition of organic matter (OM) in the following order: Mn>OM>Ni>Cd>Cu>Cr ≈? Zn>Co ≈? Fe ≈? Pb Manganese is set free faster than total organic matter. The flux balances for the total ecosystems (table 4) show input > output in the case of Cr, Fe, Cu, Cd, and Pb; input ≈? output for Ni and Zn; input < output for Mn and Co. Heavy metal stores in mineral soil are decreasing by percolation losses and increment to biomass (mainly wood) in the case of all elements investigated, except Zn (under beech), Cd and Pb (table 4). The concentrations of Cu and Pb in the forest floor layers have reached levels at which deleterious effects on microorganisms and litter decomposition are to be expected.     

Cadmium contamination of soils and rice plants caused by zinc mining

Characteristics of heavy metal contamination in paddy soils were discussed with respect to the soil and field conditions influencing the metal contents in rice.

1. In contaminated areas along the Kuzuryu River, the heavy metal contents of rice (expressed as the average of each area) were largely related to contents of paddy soils in 0.1 N HCl soluble forms as well as in total contents. A correlation was also found for the ratio of Cd to Zn in their soluble forms in the soil.

2. Within a given contaminated field plot, the heavy metal contents were not uniform, i.e: they were high around the irrigation inlet and decreased towards the outlet. However, these changes seemed to alter the Cd rice level much less than expected.

3. Soil pH and exchangeable Ca were negatively correlated with the Cd content of rice at a highly significant level. An un-drained field condition with a low soil Eh remarkably lowered the Cd content, particularly during rainy weather after the heading of the plant.

4. Based on a comparison of the extractable heavy metal contents in the waste ores and their contaminated soils, sulfide minerals derived from the mining appeared to be weathered more rapidly in the soil. With some extraction methods, the Cd origin was distinguished as the solubility of the metal in the soil among the waste products from the zinc mining and refinery.