降雨对磷基材料修复镉铅污染土壤稳定性的影响研究

通过模拟加速老化实验和土柱淋溶实验，探究降雨对磷基材料修复镉铅污染土壤效果稳定性的影响。结果表明：模拟降雨加速老化对土壤中有效镉含量的影响不显著，但是加速老化12 a后，土壤中有效铅由(2.74±0.35) mg/kg增加到(3.66±0.39) mg/kg(模拟自然降雨)和(3.59±0.19) mg/kg(模拟酸雨)。在添加磷基材料的土壤中，模拟降雨加速老化后，镉和铅有效性变化不显著。在土柱淋溶实验体系中，模拟4个月降雨当量的酸雨淋溶后，所有处理组的滤出液镉离子和铅离子始终低于0.1μg/L。对照组的表层(0～5 cm)土壤pH显著低于其他剖面层；不同剖面层土壤的镉、铅有效性和赋存形态变化较小，5～10 cm剖面层土壤的酸可溶态镉比例高于表层土壤。在添加磷基材料F、F700的处理组中，土壤pH、镉和铅的有效性与赋存形态在垂向上大多不存在显著差异，但底层(10～15 cm)土壤的酸可溶态镉和铅比例高于其他剖面层。综上所述，磷基材料能够有效固持土壤中镉和铅，削减降雨对重金属的活化-释放作用。     

硫酸盐对电子垃圾拆解地底泥中重金属形态的影响

为研究硫酸盐对重金属形态分布的影响规律,评价不同条件下的重金属生态风险,采集广东清远某电子垃圾拆解区附近河流底泥,通过投加不同浓度硫酸盐,采用BCR四步提取法分析厌氧培养28 d期间铜、铅、锌、镉的形态变化。结果表明:灭菌条件下,重金属的形态基本保持不变;在空白条件下Cu、Pb、Zn和Cd 4种重金属由不稳定态向稳定态转化,其转化率分别是7%、5%、11%和5%,锌的变化最明显;与空白相比,硫酸盐的投加会加大这4种重金属的转化,其影响顺序为:CuCdZnPb。硫酸盐的投加可促进硫酸盐还原菌的生长,当硫酸盐浓度在286~655 mg·kg-1范围时,硫酸盐还原菌的数量随着硫酸盐浓度升高而增加。实验运行到后期,高浓度的H2S会对硫酸盐还原菌产生毒害作用,因此重金属的形态并不会一直向稳定态转化,研究结果表明,高浓度硫酸盐条件可降低重金属的迁移能力,有利于重金属污染场地的修复。     

土壤重金属铅镉形态和有效态的提取方法研究

选择一步提取法(CaCl2法、NaNO3法、NH4NO3法、HCl法)提取土壤铅镉有效态含量,顺序提取法(BCR提取法、Tessier提取法)提取土壤中铅镉各形态含量。结果表明,4种一步提取法对供试土样有效态铅镉的提取效率为HCl法NH4NO3法CaCl2法NaNO3法。当镉质量浓度为0~20、40~90 mg/kg时,BCR法对土壤中镉的总提取率分别为104.9%、105.3%,Tessier法对土壤中镉的总提取率分别为101.7%、98.9%;当镉质量浓度为20~40mg/kg时,两种顺序提取法的提取效果均不佳。BCR法适合铅质量浓度为20 000~45 000 mg/kg时应用,此时BCR法对铅的总提取率为99.8%;Tessier法适合铅质量浓度为0~1 500、9 000~15 000mg/kg时应用,此时Tessier法对土壤铅的总提取率分别为100.7%、90.9%。土壤重金属铅镉各形态的含量受土壤自身pH影响不明显,但在遇到外界酸性环境影响时容易发生重金属铅镉迁移。     

生物炭-微生物复合材料修复Cr(Ⅵ)污染土壤条件优化及促生效果

生物炭和微生物在改善Cr(Ⅵ)污染土壤质量方面得到了广泛的应用,而以生物炭-微生物制备的复合材料(BC-MT)在Cr(Ⅵ)污染土壤修复中的促生效果鲜见报道。以玉米秸秆生物炭为载体吸附铬还原菌——藤黄微球菌(Micrococcus luteus)制备BC-MT,综合考察了BC-MT修复Cr(Ⅵ)污染土壤最佳条件及促生效果。结果表明:藤黄微球菌能成功附着在生物炭上,BC-MT对Cr(Ⅵ)污染土壤修复效果显著,在BC-MT投加量3%(质量分数,下同)、氮源投加量10g/kg、土壤含水率14%的条件下,修复25d,Cr(Ⅵ)去除率为64.35%,可提取态铬从27.01mg/L降至7.72mg/L。在3%BC-MT作用下,植物生长12周后地上、地下部分总铬含量分别降低了65.15%、49.76%,Cr(Ⅵ)分别降低了94.11%、87.74%,植物株高增加了17.7cm,生物量(以干重计)增加了132mg,叶绿素增加了4.65mg/g,可溶性糖增加了1.69mg/g。由此可见,BC-MT不但能有效降低土壤Cr(Ⅵ)含量,而且促生效果显著,具有广阔的应用价值。     

汞、铅、铬污染土壤的微生物修复

利用裂褶菌(Schizophyllum commune)GGHN08-116菌株,以棉籽壳、玉米秸等为固体发酵底物修复受汞、铅、铬污染的土壤。通过菌丝穿透重度重金属土壤实验,研究了菌丝在穿透土壤过程对交换态重金属的影响以及该菌株子实体对重金属离子的富集能力,同时,通过盆栽实验研究了在重度重金属污染土壤上,施用不同比例的固体发酵料对污染土壤中汞、铅、铬及其胡萝卜根茎质量、产量的影响,研究结果表明,该菌株能穿透厚度为5 cm的土壤,并有子实体生成,土壤pH值略有下降,与对照差异不显著;与对照相比,土壤中交换态汞、铬含量均显著下降,而交换态铅差异不显著,子实体中除汞含量符合标准外,铅、铬均超出了GB 7096-2003,GB 2762-2005规定标准。在固体发酵料处理下土壤中交换态汞、铅、铬含量均显著下降,胡萝卜根茎中均未检测到汞、铅含量,铬含量也符合GB 2762-2005规定标准。GGHN08-116菌株及其固体发酵产物具有修复受重金属污染土壤的能力。     

生物炭对土壤中铁生物还原作用和重金属分布的影响

构建厌氧精瓶培养实验体系,探讨生物炭对土壤中铁的生物还原和其他重金属形态转化的影响。结果表明:生物炭会影响铁还原菌希瓦氏菌(Shewanella oneidensis MR-1)对土壤中铁矿物的还原溶出,降低亚铁离子浓度。培养70d后,土壤-希瓦氏菌(SR)处理组亚铁离子摩尔浓度为(291.0±58.0)μmol/L,土壤-希瓦氏菌-生物炭(SRB)处理组亚铁离子摩尔浓度降为(94.7±32.4)μmol/L。同时,生物炭改变了铁生物还原作用对土壤中重金属迁移性的影响。SRB处理组土壤中可交换态锌、钴和镍含量低于土壤-生物炭(CB)处理组,而铁锰氧化物结合态含量增加;与SR处理组相比,SRB处理组可交换态和铁锰氧化物结合态锌、钴、镍含量均有所增加。因此,在稻田等厌氧环境下应用生物炭修复重金属污染土壤时,生物炭对铁矿物生物还原、重金属形态转化的影响需要引起关注。     

微生物矿化修复重金属污染土壤

以选矿厂附近土壤为研究对象,分析了土壤中交换态重金属含量,As、Pb、Cd、Zn和Cu的交换态浓度为14.01、4.95、0.64、33.46和12.95 mg/kg。基于生物矿化原理,利用碳酸盐矿化菌生长代谢过程产生的脲酶来分解底物尿素,产生碳酸根离子,固结重金属离子,使得土壤中活泼的重金属离子转变为碳酸盐矿物态,降低其危险。研究了温度、pH和重金属离子对酶活性的影响,发现环境30℃温度有利于促进酶活性;在弱酸性条件下,底物分解量减少15%;重金属离子在低浓度时对脲酶活性影响不大,浓度提高后对酶活性抑制作用没有加剧。将制备好的微生物矿化修复制剂喷洒于1 000 m2的污染土壤中,实验结果发现,土壤中交换态重金属离子含量在0～20 cm范围内明显减少,As、Pb、Cd、Zn和Cu的交换态浓度分别减少至2.37、1.25、0.31、16.67和3.42 mg/kg。     

胡敏素钝化修复重金属Cu(Ⅱ)、Pb(Ⅱ)污染土壤

通过土壤培养实验,研究了添加胡敏素对污染土壤中Cu、Pb生物有效性和化学形态的影响。结果表明,添加胡敏素可显著降低重金属的浸出浓度。当投加2%的胡敏素5 d后,土壤中重金属Cu~(2+)和Pb~(2+)的浸出浓度分别下降45.16%和56.97%,并且投加胡敏素10 d后对重金属的钝化基本达到稳定。尿素、硫酸铵、磷酸二氢钾可显著提高胡敏酸对Pb的钝化效果,浸出浓度分别下降了29.36%、23.57%和28.69%,但对Cu的影响不明显。进一步的研究表明,投加2%的胡敏素钝化处理30 d后土壤中交换态铜和铅的所占的比例由原来的15.68%和15.79%下降到了0.48%和1.22%,而有机态铜和铅的比例则由5.35%和10.93%上升到了13.24%和27.32%。因此,采用胡敏素作为重金属污染土壤的钝化剂具有广阔的应用前景。     

镍渣的重金属浸出特性

在分析镍渣的矿物相组成和重金属元素含量的基础上,鉴定了镍渣样品的浸出毒性,并考察了pH、液固比和浸出时间等条件对镍渣样中铬、铅、铜和锌等重金属浸出特性的影响。结果表明,镍渣中的重金属总量约为渣样的0.9%,且铬、铜和锌的含量较高,需进行安全管理。实验所用镍渣样品为第Ⅰ类一般工业固体废物。在强酸条件下镍渣中重金属浸出浓度较大,pH3后浸出浓度显著降低;液固比40 L/kg时,镍渣中重金属不断溶出,液固比40 L/kg后,浸出达到饱和,浸出浓度趋于平衡;随着浸出时间的增加,重金属离子的浸出浓度先增加后减少,但由于各重金属性质不同,各重金属达到最大浸出浓度的时间不同。     

磷改性生物炭对Pb、Cd复合污染土壤的钝化效果

中国存在着较大面积受重金属污染土壤,尤其是Pb、Cd两种重金属的复合污染较常见。利用磷改性生物炭对Pb、Cd复合污染土壤展开修复研究。结果表明:(1)磷改性生物炭可使土壤中Pb、Cd由弱酸提取态向可氧化态、残渣态转变,Pb的可氧化态和残渣态分别增加了19.4、16.9百分点,Cd的可氧化态、残渣态分别增加了17.4、9.9百分点;(2)磷改性生物炭可提高土壤有效磷,有效磷最终稳定在39 mg/kg左右;(3)磷改性生物炭能显著增加土壤阳离子交换量至19.3 cmol/kg。磷改性生物炭不仅能有效钝化重金属,还能有效改善土壤质量。     

Response of microbial activities to heavy metals in a neutral loamy soil treated with biosolid

Application of biosolid on land has been widespread in numerous countries for last several decades. This study performed incubation experiments by mixing a neutral loamy soil and biosolid enriched in Cu, Pb and Zn to explore how heavy metal affects soil mineralization and microbial biomass. The experimental results indicated that large nutrient, microorganism and C sources from biosolid were beneficial to microbial respiration. However, compared to the biosolid alone treatment, the supplemented Cu, Pb and Zn in biosolid reduced the mineralized C by roughly 36%. This phenomenon was probably caused by a portion of the Cu, Pb and Zn being complexed with organic matter to prevent decomposition of organic carbon by microorganisms. Equally, soil treated with biosolid increased the quantity of mineralized N by approximately five-fold and accelerated the rate of N mineralization by about one-fold compared to untreated soil. Notably, addition of heavy metals impaired the mineralization process, particularly when Pb reached about 64%. The reduced N mineralization occurred for similar reasons to the microbial respiration. The addition of biosolid in soil considerably increased the amount of mineralizable N; however, the increase was lower in biosolid-treated soil spiked by heavy metals. The addition of heavy metals in the soil-biosolid mixture clearly reduced the microbial biomasses C (MBC) and N (MBN), indicating that the microbial activities had been disrupted by the heavy metals. The microbial biomass C/N ratio had changed initially from 8 to 13 at the end of incubation period, owing to various groups of microbes expressing different mechanisms of metabolism, indicating that the microbial population had changed from bacteria to fungi, which had higher metal tolerance.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.     

The EDTA effect on phytoextraction of single and combined metals-contaminated soils using rainbow pink (Dianthus chinensis)

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from metal-contaminated soils. The soils used in this study were artificially added with different metals including (1) CK: original soil, (2) Cd-treated soil: 10 mg Cd kg(-1), (3) Zn-treated soil: 100 mg Zn kg(-1), (4) Pb-treated soil: 1000 mg Pb kg(-1), (5) Cd-Zn-treated soil: 10 mg Cd kg(-1) and 100 mg Zn kg(-1), (6) Cd-Pb-treated soil: 10 mg Cd kg(-1) and 1000 mg Pb kg(-1), (7) Zn-Pb-treated soil: 100 mg Zn kg(-1) and 1000 mg Pb kg(-1), and (8) Cd-Zn-Pb-treated soil: 10 mg Cd kg(-1), 100 mg Zn kg(-1), and 1000 mg Pb kg(-1). Three concentrations of 2Na-EDTA solutions (0 (control), 2, and 5 mmol kg(-1) soil) were added to the different metals-treated soils to study the influence of applied EDTA on single and combined metals-contaminated soils phytoextraction using rainbow pink. The results showed that the Cd, Zn, Pb, Fe, or Mn concentrations in different metals-treated soil solutions significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). The metal concentrations in different metals-treated soils extracted by deionized water also significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). Because of the high extraction capacity of both 0.005 M DTPA (pH 5.3) and 0.05 M EDTA (pH 7.0), applying EDTA did not significantly increase the Cd, Zn, or Pb concentration in both extracts for most of the treatments. Applying EDTA solutions can significantly increase the Cd and Pb concentrations in the shoots of rainbow pink (p<0.05). However, this was not statistically significant for Zn because of the low Zn concentration added into the contaminated soils. The results from this study indicate that applying 5 mmol EDTA kg(-1) can significantly increase the Cd, Zn, or Pb concentrations both in the soil solution or extracted using deionized water in single or combined metals-contaminated soils, thus increasing the accumulated metals concentrations in rainbow pink shoots. The proposed method worked especially well for Pb (p<0.05). The application of 2 mmol EDTA kg(-1) might too low to enhance the phytoextraction effect when used in silty clay soils.     

Effects of EDTA on solubility of cadmium, zinc, and lead and their uptake by rainbow pink and vetiver grass

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from contaminated soils. Vetiver grass (Vetiver zizanioides) has strong and long root tissues and is a potential phytostabilization plant since it can tolerate and grow well in soils contaminated with multiple heavy metals. Soil was moderately artificially contaminated by cadmium (20 mg/kg), zinc (500 mg/kg), and lead (1000 mg/kg) in pot experiments. Three concentrations of Na2-EDTA solution (0, 5, and 10 mmol/kg soil) were added to the contaminated soils to study the influence of EDTA solution on phytoextraction by rainbow pink or phytostabilization by vetiver grass. The results showed that the concentrations of Cd, Zn, and Pb in a soil solution of rainbow pink significantly increased following the addition of EDTA (p < 0.05). The concentrations of Cd and Pb in the shoots of rainbow pink also significantly increased after EDTA solution was applied (p < 0.05), but the increase for Zn was insignificant. EDTA treatment significantly increased the total uptake of Pb in the shoot, over that obtained with the control treatment (p < 0.001), but it did not significantly increase the total uptake of Cd and Zn. The concentrations of Zn and Pb in the shoots of rainbow pink are significantly correlated with those in the soil solution, but no relationship exists with concentrations in vetiver grass. The toxicity of highly contaminating metals did not affect the growth of vetiver grass, which was found to grow very well in this study. Results of this study indicate that rainbow pink can be considered to be a potential phytoextraction plant for removing Cd or Zn from metal-contaminated soils, and that vetiver grass can be regarded as a potential phytostabilization plant that can be grown in a site contaminated with multiple heavy metals.     

The effects of soil amendments on heavy metal bioavailability in two contaminated Mediterranean soils

Two heavy metal contaminated calcareous soils from the Mediterranean region of Spain were studied. One soil, from the province of Murcia, was characterised by very high total levels of Pb (1572 mg kg(-1)) and Zn (2602 mg kg(-1)), whilst the second, from Valencia, had elevated concentrations of Cu (72 mg kg(-1)) and Pb (190 mg kg(-1)). The effects of two contrasting organic amendments (fresh manure and mature compost) and the chelate ethylenediaminetetraacetic acid (EDTA) on soil fractionation of Cu, Fe, Mn, Pb and Zn, their uptake by plants and plant growth were determined. For Murcia soil, Brassica juncea (L.) Czern. was grown first, followed by radish (Raphanus sativus L.). For Valencia soil, Beta maritima L. was followed by radish. Bioavailability of metals was expressed in terms of concentrations extractable with 0.1 M CaCl2 or diethylenetriaminepentaacetic acid (DTPA). In the Murcia soil, heavy metal bioavailability was decreased more greatly by manure than by the highly-humified compost. EDTA (2 mmol kg(-1) soil) had only a limited effect on metal uptake by plants. The metal-solubilising effect of EDTA was shorter-lived in the less contaminated, more highly calcareous Valencia soil. When correlation coefficients were calculated for plant tissue and bioavailable metals, the clearest relationships were for Beta maritima and radish.     

雷州半岛土壤重金属分布特征及其污染评价

在雷州半岛采集了106个土壤表层样品,分析了其中8种重金属元素(Cu、Pb、Zn、Cr、Ni、Cd、Hg和As)的全量.结果表明,雷州半岛土壤重金属污染由高到低排序为Ni＞Cr＞Hg＞Cu＞Zn＞Cd＞As＞Pb,Zn、Cd、As和Pb质量浓度均没有超标,Hg和Cu质量浓度超标率亦不高,但Ni和Cr平均质量浓度达49.81、87.13 mg/kg,高于国内外其他对照区域,超标率分别为25.47%和24.53%;重金属元素在雷州半岛各土壤利用类型中分布规律不明显,按4种主要土壤利用类型受重金属污染程度大小排序为甘蔗地＞果园土＞水田＞菜地;雷州半岛土壤综合污染指数总平均为0.970,土壤总体上尚清洁,重金属污染处于警戒水平;雷州半岛各区域中,徐闻、雷州两地土壤重金属质量浓度明显高于其他地区,其主要原因是徐闻、雷州两地成土母质主要为玄武岩,造成土壤Cr、Ni及其他重金属背景值较高.     

Zn, Cd and Pb accumulation and arbuscular mycorrhizal colonisation of pennycress Thlaspi praecox Wulf. (Brassicaceae) from the vicinity of a lead mine and smelter in Slovenia

Significant hyperaccumulation of Zn, Cd and Pb in field samples of Thlaspi praecox Wulf. collected from a heavy metal polluted area in Slovenia was found, with maximal shoot concentrations of 14,590 mg kg(-1) Zn, 5960 mg kg(-1) Cd and 3500 mg kg(-1) Pb. Shoot/root ratios of 9.6 for Zn and 5.6 for Cd show that the metals were preferentially transported to the shoots. Shoot bioaccumulation factors exceeded total soil Cd levels 75-fold and total soil Zn levels 20-fold, further supporting the hyperaccumulation of Cd and Zn. Eighty percent of Pb was retained in roots, thus indicating exclusion as a tolerance strategy for Pb. Low level colonisation with arbuscular mycorrhizal fungi (AMF) of a Paris type was observed at the polluted site, whereas at the non-polluted site Arum type colonisation was more common. To our knowledge this is the first report of Cd hyperaccumulation and AMF colonisation in metal hyperaccumulating T. praecox.     

Arrested municipal solid waste incinerator fly ash as a source of heavy metals to the UK environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators in the UK have been analysed for a range of elements. Some of the more important heavy metals ranged in concentration as follows: Cd, 21-4646 (median = 271) mg kg(-1); Cu, 296-1307 (642) mg kg(-1); Cr, 44-1328 (574) mg kg(-1); Ni, 45-2204 (74) mg kg(-1); Pb, 447-9704 (4337) mg kg(-1); and Zn, 2285-13,500 (9232) mg kg(-1). These concentrations represent considerable enrichments relative to median UK soil concentrations. Enrichment ratios (defined as median fly ash: median UK soil) were as follows: Mn 1.6; Co 2.6; Ni 3.3; Ba 11; Sr 11; Cr 15; Cu 35; Pb 108; Zn 113; Cd 387. It is estimated that MSW incinerator ash contributes c. 15 t Cd and 241 t Pb to UK landfill sites per annum. These figures compare with previous studies by Hutton & Symon (Hutton, M. & Symon, C. (1986). The quantities of cadmium, lead, mercury and arsenic entering the UK environment from human activities. Sci. Total Environ., 57, 129-50.) which estimated that annual inputs to UK landfills from coal fly ash are c. 60 t Cd and 1270 t Pb. However, it is argued that metals associated with MSW ashes are potentially of greater environmental significance than in coal ashes, because they are much more available and present at much higher concentrations.     

Comparative tolerance of Pinus radiata and microbial activity to copper and zinc in a soil treated with metal-amended biosolids

A study was conducted to evaluate the effects of elevated concentrations of copper (Cu) and zinc (Zn) in a soil treated with biosolids previously spiked with these metals on Pinus radiata during a 312-day glasshouse pot trial. The total soil metal concentrations in the treatments were 16, 48, 146 and 232 mg Cu/kg or 36, 141, 430 and 668 mg Zn/kg. Increased total soil Cu concentration increased the soil solution Cu concentration (0.03–0.54 mg/L) but had no effect on leaf and root dry matter production. Increased total soil Zn concentration also increased the soil solution Zn concentration (0.9–362 mg/L). Decreased leaf and root dry matter were recorded above the total soil Zn concentration of 141 mg/kg (soil solution Zn concentration, >4.4 mg/L). A lower percentage of Cu in the soil soluble?+?exchangeable fraction (5–12 %) and lower Cu²⁺ concentration in soil solution (0.001–0.06 μM) relative to Zn (soil soluble?+?exchangeable fraction, 12–66 %; soil solution Zn²⁺ concentration, 4.5–4,419 μM) indicated lower bioavailability of Cu. Soil dehydrogenase activity decreased with every successive level of Cu and Zn applied, but the reduction was higher for Zn than for Cu addition. Dehydrogenase activity was reduced by 40 % (EC₄₀) at the total solution-phase and solid-phase soluble?+?exchangeable Cu concentrations of 0.5 mg/L and 14.5 mg/kg, respectively. For Zn the corresponding EC₅₀ were 9 mg/L and 55 mg/kg, respectively. Based on our findings, we propose that current New Zealand soil guidelines values for Cu and Zn (100 mg/kg for Cu; 300 mg/kg for Zn) should be revised downwards based on apparent toxicity to soil biological activity (Cu and Zn) and radiata pine (Zn only) at the threshold concentration.     

Contamination of wild-grown edible mushrooms by heavy metals in a former mercury-mining area

The aim of this study was to evaluate the contamination of six edible wild species of mushrooms (Boletus pulverulentus, Cantharellus cibarius, Lactarius quietus, Macrolepiota procera, Russula xerampelina and Suillus grevillei) by heavy metals (Hg, Cd, Pb, Zn, Cu, Ni, Cr, Co, Mn and Fe). Mushroom samples were collected from sites contaminated by emissions from mining and processing of polymetallic ores in operation during the period 1969–1993 in Rudňany, southeast Slovakia. The four study sites spanned up to a 5-km distance from the emission source. The collected mushroom samples were analyzed using Flame Atomic Absorption Spectrophotometry and/or Flame Atomic Absorption Spectrophotometry with graphite furnace. Mercury, Cd and, in some samples, also Pb present the highest risks in terms of contamination of the food chain following subsequent consumption. The content of two metals in the dry matter (dm) of the mushrooms exceeded the limits set by the European Union (EU; Cd: 0.5 mg/kg dm, Pb: 1.0 mg/kg dm). The highest mean contents of the eight metals recorded for S. grevillei were 52.2, 2.15, 107, 104, 2.27, 2.49, 81.6 and 434 mg/kg dm for Hg, Pb, Zn, Cu, Ni, Cr, Mn and Fe, respectively. The highest content of Cd was recorded in M. procera (3.05 mg/kg dm) and that of Co in L. quietus (0.90 mg/kg dm). The calculated weekly intake for Hg, Pb and Cd shows that regular consumption of mushrooms from the studied area poses risks to human health.