Environmentally significant photochemistry of chlorinated benzenes and their derivatives in aquatic systems†

The pollution of soil and aquatic environments by chlorinated aromatic pollutants (CAPs) such as polychlorobenzenes (PCBzs), polychlorophenols (PCPs), polychloro‐diphenyl ethers (PCDPEs), phenoxyacetic acids, etc., creates growing public anxiety. Phototransformation is an important process for pollutants in aquatic systems. This article extensively reviews the environmentally significant solution phase photochemistry of PCBzs as well as other CAPs derived therefrom. The paper includes photochemical fate of these CAPs at wavelengths >285 nm on the one hand and their photolysis in solution in aquatic systems on the other. In this article, photolytic reductive dechlorination and isomerization of PCBzs are reviewed together with the photoformation of several products including polychlorobiphenyls (PCBs) from PCBzs. Recently developed phenomena of photoincorporation of PCBzs into humic model monomers is also described. This review also describes the environmental photochemistry of chlorobenzene derivatives, namely, α‐substituted p‐chlorotoluenes of the general structure p‐ClC₆H₄CH₂‐X (X = H, Cl, CN, COOH and OH), di‐through pentachlorophenols, PCDPEs (having Cl_1–5 contents) with and without o‐OH substituents, and 2,4‐di‐ and 2,4,5‐trichlorophenoxyacetic acid (2,4‐D and 2,4,5‐T, respectively) as well as their esters and some formulations.     

Irrigation with domestic wastewater: responses on growth and yield of ladyfinger Abelmoschus esculentus and on soil nutrients

Domestic wastewater is generated continuously and in large quantities. It can serve as an alternative water nutrient source for irrigation. In the present study Abelmoschus esculentus L. (Ladyfinger) was irrigated using untreated wastewater (T1), treated wastewater (T2) and rainwater (T3) in pot experiments. The effect was seen on nutrient fortication, growth and yield of the plant and the nutrient status of the soil. Additionally the build up of Cr, Cu and Zn from the irrigation water were anlayzed in different parts of the plant biomass and in the soil. The sapling survival rate was found to be 87% in T1 followed by T2 and T3. Root shoot ratio under different treatments was found in the order T3 (0.46) >T2 (0.35) >T1 (0.31). The chlorophyll a, b and carotene content in the leaves (mg g(-1)) was found to be 6.3, 0.5, 0.9 under T1, 4.8, 0.4, 0.8 under T2 and 3.2, 0.3, 0.5 under T3 respectively and all the three varied in the order T1>T2>T3. The same trend was found in case of total dry matter (g) T1 (6.3) >T2 (3.7) >T3 (2.3) at p < or = 0.05. There was a considerable increase in nutrients in the soil under T1 and T2 as compared to T3 after final harvest. The organic matter (%), NO3-N and PO4(3-) (mg kg(-1)) content post harvest soil was found to be 3.4, 71, 90 under T1 and 2.9, 52, 63 under T2 respectively. Also, there was an increase in cations Na, K, Ca and Mg in the soil irrigated with T1 and T2 after the final harvest. Thus irrigation with wastewater generally increased soil fertility. Only a small percentage of the heavy metal was bioaccumulated by the plant parts from the irrigation water. There was hardly any metal accumulation in fruits. Bulk of the metal ions remained in the soil.     

Tessaria absinthioides: a possible bio‐monitor for Cd,Pb, and Cu,in the middle and lower basin of the loa river,North Chile

Some ecotoxic metals such as Cd, Pb, and Cu in Tessaria absinthioides were quantified to study its possible use as a bio‐indicator and/or bio‐monitor of these metals. This plant was chosen for its abundance in the area under study, along Chile and even in southern Latin America. For Cd, Pb, and Cu in all three parts of the plant (leaves, stems and roots) a different concentration pattern in each sampling areas was observed. In sampling areas Coya Sur and La Cascada copper and cadmium concentration decrease in order: leaves > roots > stems. In samples collected in Xalquincha the lowest concentrations of Cd and Pb were observed in stems. A maximum of cadmium concentration (9ug/gd.w. in leaves) was found in samples from La Cascada, a inflow to river Loa in Calama. High concentrations of lead were found in roots and leaves. Collected data demonstrate that the main pathway for cadmium is from ground water via roots into the plant. Some data obtained for lead and copper indicate that the influence of dust particles adsorbed on leaves and stems can be higher than uptake from ground water.     

除草剂对强筋小麦产量及生理特性的影响

在盆栽和大田条件下,研究4种除草剂对2个强筋小麦品种(“临优145”和“临汾138”)产量及生理特性的影响.结果表明,在推荐用量下,除草剂对成穗数、穗粒数和穗长的影响较小,对株高、千粒重、旗叶叶绿素相对含量(SPAD值)、净光合速率及灌浆进程影响较大.2,4-D丁酯使旗叶SPAD值、净光合速率一直较低,千粒重降低;“巨星”在灌浆前期使旗叶SPAD值、净光合速率保持较高,灌浆中后期快速下降,并使灌浆持续时间相对缩短,千粒重最低,较对照分别低2.40g和0.84g;而“世玛”使灌浆前中期SPAD值和净光合速率较低,但下降相对缓慢,使灌浆持续时间分别延长3.48d和1.86d,“库”容增加,千粒重分别提高1.18g和1.05g,同时具有一定的降低株高作用;“骠马”虽使灌浆持续时间延长,但影响相对较小.除草剂对籽粒生长模型参数的影响,品种间存在一定差异,除草剂对“临优145”初始生长势、快增期和缓增期持续时间、快增期和缓增期平均灌浆速率影响较大,而对“临汾138”的这些指标以及总灌浆持续时间影响较大.分析旗叶光合特性、灌浆进程、千粒重及产量间的相关性,表明除草剂主要是通过旗叶生理和灌浆进程来影响千粒重和产量.图1表7参19     

Lichen Conservation in Heavily Managed Boreal Forests

Lichens are an important component of the boreal forest, where they are long lived, tend to accumulate in older stands, and are a major food source for the threatened woodland caribou (Rangifer tarandus caribou). To be fully sustainable, silvicultural practices in the boreal forest must include the conservation of ecological integrity. Dominant forest management practices, however, have short‐term negative effects on lichen diversity, particularly the application of herbicides. To better understand the long‐term effects of forest management, we examined lichen regeneration in 35 mixed black spruce (Picea mariana) and jack pine (Pinus banksiana) forest stands across northern Ontario to determine recovery following logging and postharvest silvicultural practices. Our forest stands were 25–40 years old and had undergone 3 common sivilcultural treatments that included harvested and planted; harvested, planted, and treated with N‐[phosphonomethyl] glycine (glyphosate); and harvested, planted, and treated with 2,4‐dichlorophenoxyacetic acid (2,4‐D). Forest stands with herbicide treatments had lower lichen biomass and higher beta and gamma diversity than planted stands that were not treated chemically or control stands. In northwestern Ontario, planted stands that were not treated chemically had significantly greater (p < 0.05) alpha diversity than stands treated with herbicides or control stands. Our results show that common silvicultural practices do not emulate natural disturbances caused by wildfires in the boreal forest for the lichen community. We suggest a reduction in the amount of chemical application be considered in areas where lichen biomass is likely to be high and where the recovery of woodland caribou is an objective. Conservación de Líquenes en Bosques Boreales Manejados Intensivamente     

内生真菌感染对黑麦草若干抗旱生理特征的影响

对周期性干旱胁迫下内生真菌感染（EI）和非感染（EF）的黑麦草植株的几项生理指标进行了比较。结果表明，干旱胁迫导致EI和EF叶片相对水分含量下降，细胞膜透性增加，游离脯氨酸累积，叶绿素，类胡萝 纱和淀粉含量下降，可溶性糖含量增加，与EF植株相比，干旱胁迫下EI植株可溶性糖含量较高，膜透性及脯氨酸含量均较低，从生理生化角度说明内生真菌可提高其宿主植物的抗旱性。图3参39     

绿黄隆、甲黄隆在江苏省农区5种土壤中残留活性的研究

采用改进的玉米主根长土培生测法，研究绿黄隆、甲黄隆在江苏省典型农区土壤中残留活性。结果表明，两种除草剂在５种土壤中剂量与玉米主根长抑制率之间皆达极显著相关，土壤ｐＨ和有机质含量是主要影响因素，碱性轻质土壤中活性较高，酸性重质土壤中活性较低，活性大小顺序为：黄潮土＞高沙土＞砂姜黑土＞滨海盐土＞太湖水稻土。     

2,4-D二甲胺盐对莲草直胸跳甲生存和繁殖的影响

为探究除草剂在防治喜旱莲子草(Alternanthera philoxeroides)的过程中对其天敌昆虫的影响,采用不同浓度的2,4-D二甲胺盐浸叶处理的喜旱莲子草饲喂莲草直胸跳甲,连续饲喂7d后,考察了莲草直胸跳甲的繁殖、存活和发育情况。结果表明,2,4-D二甲胺盐可显著降低莲草直胸跳甲成虫的取食量,且抑制作用随药剂浓度升高和取食时间延长而显著增强;较高浓度(1.72～3.44g·L~(-1))的2,4-D二甲胺盐还会导致莲草直胸跳甲雌成虫存活率和产卵量的明显降低,卵孵化率、幼虫存活率和蛹羽化率也显著降低。可见,高浓度(1.72～3.44g·L~(-1))的2,4-D二甲胺盐对莲草直胸跳甲的生长发育和繁殖有显著不利影响,在防治喜旱莲子草时,应将2,4-D二甲胺盐的施用浓度控制在0.22～0.86g·L~(-1)内。     

Abstracts to forthcoming papers

Soil and sediments collected at a former chlor‐alkali plant in coastal Georgia (United States), revealed the presence of PCDF concentrations as great as 82.3 ng/g, dry wt. PCDF congener profile in soil was typical of “chlorine pattern”; with elevated proportions of OCDF and HpCDF. Concentrations of PCDFs declined gradually by 44‐fold at a distance of about 500 m along the contamination gradient. Of PCDDs/DFs, 2,3,7,8‐substituted PCDFs accounted for 94–98% of the TCDD‐like activity, which declined by 25‐fold, corresponding with the reduction of total PCDF concentrations. Concentrations of PCDDs in sediments were as great as 17 ng/g, with an elevated contribution from OCDD. The magnitude of decline in PCDD concentrations with distance from the source was less pronounced than that for PCDFs. PBDDs and PBDFs were not detected. Polybrominated biphenyl ether (PBBE) and monobromo‐heptachloro dibenzo‐p‐dioxins and dibenzofurans (PXDDs/DFs) were found, though, at low concentrations. Their spatial distribution was similar to those of PCDDs.     

Commercial phenoxyacetic herbicides control heavy metal uptake by wheat in a divergent way than pure active substances alone

Background

Impact of two widely used commercial herbicides, i.e. Aminopielik D 450 SL and Chwastox 300 SL, on the uptake and translocation of selected heavy metals in wheat plants Triticum aestivum L. cultivated in the laboratory pot experiments was investigated. Mineral-humus, loamy sand soil representative for the central part of Poland was applied. Bioavailable, exchangeable and total forms of Cd, Co, Cu, Zn, Pb, and Mn were determined. Transfer coefficients, translocation, and bioaccumulation factors illustrating metal migration in the plant were investigated.

Results

Administration of commercial herbicides significantly altered heavy metals uptake by wheat in a way distinctively different than that observed for the parent chemically pure synthetic auxins, i.e. 2,4-D and MCPA. In particular, Aminopielik D 450 SL and Chwastox 300 SL prompted heavy metals accumulation in roots as indicated by their high transfer coefficients. Further transport to above ground part of the plant was limited and element dependent.

Conclusions

This work clearly shows that commercial herbicide formulations may act in a distinctively different way than pure active ingredients alone.

     

铅处理对茴香植株生长及精油组分的影响

为了揭示铅对茴香（Foeniculum vulgare L.）生长和次生代谢产物-精油组分的影响及茴香植株对铅的吸收累积特性,本试验采用水培方法,在霍格兰营养液中加入铅,设计0（对照）、1 mg·L^-1、5 mg·L^-1、10 mg·L^-1处理,研究了不同铅质量浓度对茴香植株生长、精油组分及茴香植株对铅吸收累积的影响。结果表明：不同铅质量浓度处理对茴香植株的形态、生物量、色素质量分数、碳和氮质量分数、铅的吸收累积及精油组分均有影响。随着铅质量浓度的增加,茴香植株的株高呈降低趋势,且各处理之间差异显著,真叶数大致也呈降低趋势,但仅10 mg·L^-1处理显著低于对照,各处理的最大叶长差异均不显著,最大叶宽仅对照与5 mg·L^-1处理之间差异显著。随着铅质量浓度的增加,地上部鲜质量和干质量均呈逐渐降低趋势,且铅处理后的地上部鲜质量和干质量均显著低于对照,地下部鲜质量和干质量呈逐渐升高趋势,但铅处理后的地下部鲜质量和干质量与对照差异均不显著,根冠比呈逐渐增加趋势,但仅10 mg·L^-1处理显著高于对照。随着铅质量浓度的增加,叶绿素a、叶绿素b、叶绿素a＋b和类胡萝卜素质量分数均呈降低趋势,且均低于对照,叶绿素a/叶绿素b以5 mg·L^-1处理最高,但仅显著高于1 mg·L^-1处理。铅处理后,可溶性蛋白质质量分数均高于对照,但仅1 mg·L^-1处理和5 mg·L^-1处理显著高于对照,全氮质量分数与可溶性蛋白质质量分数的变化趋势基本一致,但各处理之间差异均不显著;随铅质量浓度的增加,可溶性糖质量分数呈降低趋势,除1 mg·L^-1处理显著高于对照外,其余铅处理均显著低于对照,各处理的全碳质量分数与对照差异均不显著。随铅质量浓度的增加,茴香植株对铅的吸收累积显著增加。不同铅质量浓度处理下的反式-茴香脑含量和含氧化合物均显著低于对照,以5 mg·L^-1铅处理最低,而柠檬烯含量和单萜类化合物均显著高于对照,以5 mg·L^-1铅处理最高;随铅质量浓度的增加,倍半萜类化合物含量呈降低趋势,且均低于对照。因此,铅能抑制茴香植株的生长;随铅质量浓度的增加,茴香植株对铅的吸收累积显著增加;铅处理能影响茴香精油组分,显著降低反式-茴香脑和含氧化合物含量,而显著提高柠檬烯和单萜类化合物含量。     

Aufnahme von 2,4,6-Trinitrotoluol in Pflanzen

Soil contaminations with the explosive 2,4,6-TNT are a major problem at many sites of former ammuniton plants in Germany. But only little is known about its environmental or metabolic fate in soil or plants. A field study was conducted on a former ammunition plant in Stadtallendorf/Hessen. Three areas with different TNT concentrations were planted with 8 different crops. After harvest plants were analyzed for TNT, ADNTs and DNTs. Soil contamination decreased in the rhizosphere compared to unplanted areas and there was a transfer of TNT from soil to the plants. Accumulation in plants was dependent on soil contamination and also specific for different plant parts or plant species. The contamination spectrum of TNT and derivatives was different in soil or plant tissue, respectively. After acid hydrolysis of bean roots, 2,6-DNT and 2,4-DNT could be identified in the extract.     

Effects of copper (I) oxide on growth and biochemical compositions of two marine microalgae

In copper based antifouling (AF) paints Cu (I) oxide was largely used as booster biocide. In this study effect of Cu (I) oxide on two marine microalgae, Tetraselmis suecica and Dunaliella tertiolecta was demonstrated. EC50 (96 hr) concentrations estimated for T. suecica and D. tertiolecta were 1.3 mg l(-1) and 1.34 mg l(-1), respectively. Copper (I) oxide induced changes in growth, chlorophyll, carbohydrate and protein contents were observed in T. suecica and D. tertiolecta. At low concentration of 0.0625 mg l(-1), 3-26% and 1-16% growth stimulation was observed in T. suecica and T. tertiolecta respectively. Increasing Cu (I) oxide concentrations proportionately decreased the carbohydrate and protein contents. This study clearly indicates the toxicity of excessive Cu (I) oxide on growth and biochemical compositions of T. suecica and D. tertiolecta.     

除草剂对优质小麦品质和旗叶保护酶的调控效应

通过田间试验研究了4种除草剂在正常剂量下对2个优质小麦品种品质性状、蛋白质组分和旗叶保护酶系的影响.结果表明,整个籽粒灌浆过程中,2,4-D丁酯处理使籽粒蛋白质含量一直较高,世玛处理在灌浆前中期籽粒蛋白质含量较高,但灌浆末期籽粒蛋白质含量最低,巨星和骠马处理影响较小.2,4-D丁酯处理使收获时籽粒蛋白质含量及组分最高,湿面筋含量、沉降值、吸水率、稳定时间和评价值等加工品质最好,世玛处理则使营养品质和加工品质最差,巨星和骠马处理影响相对较小.籽粒灌浆期间,2,4-D丁酯处理使旗叶SOD、CAT和POD活性一直较低,尤其是籽粒灌浆末期活性最低;其它除草剂使旗叶SOD、CAT和POD活性在不同灌浆时期存在差异:灌浆前中期,骠马处理使3种保护酶活性最高;灌浆后期,世玛处理使旗叶中保护酶活性下降缓慢,且活性最高.籽粒灌浆期前期,4种除草剂对旗叶中MDA含量的影响是:世玛＞骠马＞CK＞巨星＞2,4-D丁酯,灌浆中后期,2,4-D丁酯和巨星处理使MDA含量快速提高,世玛和骠马处理使MDA含量升高相对较慢,到灌浆末期,2,4-D丁酯使MDA含量最高,世玛处理最低.图5表2参22     

藿香蓟(Ageratum conyzoides)对土壤铅胁迫的生理响应

为了解日益增加的城市土壤铅(Pb)胁迫对城市园林地被植物的影响,采用盆栽实验研究土壤Pb胁迫对藿香蓟(Ageratum conyzoides)叶片生理特性的影响.结果显示,Pb胁迫处理降低了藿香蓟叶片的叶绿素总量及叶绿素a和b含量,质膜透性增大,丙二醛(MDA)含量上升.随着Pb浓度增加,同一时期内藿香蓟叶片SOD、POD和CAT酶活性均上升,但土壤Pb浓度超过750 mg kg-1或1 000 mg kg-1后保护酶活性开始逐渐下降.随着胁迫处理时间的延长,SOD活性在d 20、d 40和d 60时都高于胁迫处理d 7时的活性,POD活性是在d 20时急剧下降,CAT活性则在胁迫处理d 60时急剧下降.研究表明,藿香蓟能在一定程度上适应土壤Pb胁迫,但Pb胁迫浓度超过750 mg kg-1后将影响其生理代谢过程.图4参20     

Accumulation, tolerance and impact of aluminium, copper and zinc on growth and nitrate reductase activity of Ceratophyllum demersum (Hornwort)

Ceratophyllum demersum (homwort) was subjected to toxic concentrations of Al (3 and 9 mg l(-1)), Zn (3 and 9 mg l(-1)) and Cu (2.5 and 7 mg l(-1)) in culture solutions for 15 days. The higher dose of Al enhanced the chlorophyll content significantly (p<0.05) in the first 6 days of treatment while other treatments caused marked reductions. Nitrate reductase activity (NRA) was significantly reduced (p<0.05) byAl, Cu and Zn toxicity and ceased completely in plants treated with Cu by the 6th day of treatment. Dry biomass and relative growth rate were reduced significantly (p<0.05) by metal treatment. Tolerance index of the plant was low for Cu (21.62 and 13.43% at low and high doses, respectively) and moderate for Zn (63.74 and 54.85%) and Al (72.83 and 68.79%). Accumulation ofAl, Zn and Cu was threefold at higher doses compared with the lower doses but the bioconcentration factors (BCF) were very low indicating that this plant is not a hyper accumulator of these metals.     

High level of nickel tolerance and metal exclusion identified in silver maple (Acer saccharinum)

Nickel (Ni) and copper (Cu) are the most prevalent metals found in the Greater Sudbury Region ecosystems. The main objectives of this study are to (1) assess silver maple (Acer saccharinum) tolerance to different doses of Ni and (2) determine the translocation pattern of metals in A. sacharinum. This study revealed that A. sacharinum is highly tolerant to high doses of NI (1600 and 9200?mg/kg). Growth chamber screening trials revealed that Ni is stored in roots and does not translocate to other plant parts. Analysis of samples from A. sacharinum growing for >30 years in soil contaminated with metals also showed that the levels of iron (Fe), manganese (Mn), Ni, and zinc (Zn) were significantly higher in roots compared with soils and aerial parts. On the other hand, the amount of Cu was higher in soil compared with roots and other plant parts. In fact, the bioaccumulation factors (BFs) were 0.29, 2.00, 3.6, 1.9, and 4.0 for Cu, Fe, Mn, Ni, and Zn, respectively. The translocation from roots to aerial parts showed an insignificant level of movement of Cu, Fe, and Ni. Hence, A. saccharinum is classified as excluder for Fe, Mn, Ni, and Zn, and avoider for Cu.     

Influence of pH on lead uptake, chlorophyll and nitrogen content of Nasturtium officinale R. Br. and Mentha aquatica L

In the present study, effects of pH (5.0, 7.0 and 9.0) and lead (1, 5, 10, 25, 50 and 100 microg mL(-1)) were investigated on uptake of lead, content of chlorophyll and nitrogen in Nasturtium officinale and Mentha aquatica. Total chlorophyll and nitrogen contents were adversely affected from Pb2+ concentrations dose dependently at each pH. The macrophytes were adversely affected by pH 5.0 or more than 9.0. After 12-days Pb2+ treatment, results showed that lead accumulation of macrophyte tissues was variable. According to the parts of the macrophytes, Pb2+ amounts were generally found at all tested pH levels and the metal concentrations for M. aquatica in the following order: root > stem > leaf and for N. officinale root > leaf > stem. Pb2+ concentrations in plant tissues (root, stem, leaf) in relation to pH were generally found for both macrophytes in following order: 7.0 > 9.0 > 5.0. Despite of the fact that high Pb2+ accumulation was observed in root tissues of the macrophytes, low metal accumulation was measured in the above-ground parts indicating low root-leaf translocation. The study indicated that uptake rate of Pb2+ and its toxicity on Chlorophyll and nitrogen contents in the macrophytes were dependent upon pH value of solutions.     

HgCl2对斜生栅藻（Scenedesmus obliquus）生理生化特性的影响(Effects of HgCl2 on Physiological and Biochemical Characteristics of Scenedesmus obliquus)

为探讨汞对藻类的毒性效应,以斜生栅藻(Scenedesmus obliquus)为实验材料,检测了HgCl2对藻细胞数目、光合色素含量、超氧化物歧化酶(SOD)活性、丙二醛(MDA)含量等生化指标的影响.结果表明,各暴露组(0.2～1.5mg·L-1)HgCl2对斜生栅藻的生长均有抑制作用,随HgCl2暴露浓度的增大,藻细胞密度逐渐降低,HgCl2对斜生栅藻的48、72、96hEC50值分别为1.194、1.113、0.986mg·L-1.随着HgCl2暴露浓度的升高(0.01～1.5mg·L-1),叶绿素a、b及类胡萝卜素等光合色素含量均呈逐渐降低趋势;SOD活性表现为先激活后抑制;MDA含量则显著增加(p<0.05,p<0.01).     

四种除草剂对泥鳅红细胞遗传毒性的研究

采用红细胞微核和核异常测试法,研究了除草剂精禾草克、氟乐灵、扫茀特,2-甲-4氯钠水剂对泥鳅红细胞核的遗传毒性.结果表明,4种除草剂单独作用时均不同程度地引起微核细胞率和核异常细胞率等遗传指标的上升(P<0.05或P<0.01). 低浓度的除草剂对泥鳅红细胞的联合诱变作用比高浓度的除草剂明显.除草剂浓度与微核率或核异常率无显著相关,不表现剂量-效应关系.扫茀特的诱变效应大于其它3种除草剂.4种除草剂联合作用时具拮抗性. 图1 表5 参20