Organochlorine pesticides and polychlorinated biphenyl residues in reared and wild Dicentrarchus labrax from the Mediterranean Sea (Sicily, Italy)

The aim of this research was to compare the levels of organochlorine pesticides and PCBs in samples of Dicentrarchus labrax living in the Straits of Messina with samples cultivated in cages in the Mediterranean Sea. Muscles and liver tissues sampled over the months, within the same year, were analyzed. The quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC–MS. The results showed that the concentrations of DDTs in muscles and livers as such of reared sea bass were in the range 0.2–1.3 μg/kg and 9.6 –48.4 μg/kg, respectively. In wild fish the concentrations of DDTs were very much lower: 0.1 μg/kg in muscles, 5.1–9.0 μg/kg in livers. Total PCBs levels were higher in cultivated sea bass than in wild fish; the concentration ranges were 5.3–59.7 μg/kg and 74.4–267.4 μg/kg in muscle and liver of reared samples, respectively, and 1.1–1.5 μg/kg and 63.2–109.4 μg/kg in muscle and liver of wild samples, respectively.     

固相萃取-高效液相色谱法测定水中呋喃丹、甲萘威和阿特拉津

采用固相萃取-高效液相色谱(SPE - HPLC)二极管阵列检测器同时测定水中呋喃丹、甲萘威和阿特拉津,以甲醇-水为流动相,采用梯度洗脱方式,选择220 nm为检测波长,二氯甲烷为洗脱剂.呋喃丹在0.200 mg/L ～5.00 mg/L、甲萘威和阿特拉津在0.020 mg/L～5.00 mg/L范围内线性良好,检出限...     

The concentrations, distribution and sources of PAHs in agricultural soils and vegetables from Shunde, Guangdong, China

The concentrations, distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in 30 agricultural soil and 16 vegetable samples collected from subtropical Shunde area, an important manufacturing center in China. The total PAHs ranged from 33.7 to 350 μg/kg in soils, and 82 to 1,258 μg/kg in vegetables. The most abundant individual PAHs are phenanthrene, fluoranthene, chrysene, pyrene and benzo(b)fluoranthene for soil samples, and anthracene, naphthalene, phenanthrene, pyrene and chrysene for vegetable samples. Average vegetable–soil ratios of total PAHs were 2.20 for leafy vegetables and 1.27 for fruity vegetables. Total PAHs in vegetable samples are not significantly correlated to those in corresponding soil samples. Principal component analyses were conducted to distinguish samples on basis of their distribution in each town, soil type and vegetable specie. Relatively abundant soil PAHs were found in town Jun’an, Beijiao, Chencun, Lecong and Ronggui, while abundant vegetable PAHs were observed in town Jun’an, Lecong, Xingtan, Daliang and Chenchun. The highest level of total PAHs were found in vegetable soil, followed by pond sediment and “stacked soil” on pond banks. The PAHs contents in leafy vegetables are higher than those in fruity vegetables. Some PAH compound ratios suggest the PAHs derived from incomplete combustion of petroleum, coal and refuse from power generation and ceramic manufacturing, and paint spraying on furniture, as well as sewage irrigation from textile industries. Soil PAHs contents have significant logarithmic correlation with total organic carbon, which demonstrates the importance of soil organic matter as sorbent to prevent losses of PAHs.     

Plant Uptake/Bioavailability of Heavy Metals from the Contaminated Soil after Treatment with Humus Soil and Hydroxyapatite

Cellulose nitrate membrane filter was used for the preconcentration-separation of Cu, Co, Cd, Pb and Cr ions. The analyte ions were collected on the membrane filter by the aid of carmine. Then membrane filter was dissolved by using nitric acid. The levels of the analytes in the final solutions were determined by flame atomic absorption spectrometry (FAAS). The analytical parameters including pH, amounts of carmine, sample volumes etc. have been optimized. No influences have been observed from the matrix ions. The detection limits for analytes were in the range of 0.08 μg/l-0.93 μg/l. The validation of the procedure was checked by the analysis of standard reference sediment (GBW 07309). The present method has been successfully applied for the FAAS determinations of analyte ions in real samples including black tea and magnesium salts.     

Persistent Organochlorine Pesticide Residues in Soil and Surface Water of Northern Indo-Gangetic Alluvial Plains

This study reports the concentration levels and distribution pattern of the organochlorine pesticide (OCPs) residues in the soil and surface water samples collected from the northern Indo-Gangetic alluvial plains. A total of 31 soil and 23 surface water samples were collected from the study region in Unnao district covering an area of 2150 km² and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (α and β), endosulfan sulfate, heptachlor and its metabolites, α-chlordane, γ-chlordane and methoxychlor. In both the soil and surface water samples β- and δ-isomers of HCH were detected most frequently, whereas, methoxychlor was the least detected pesticide. The results showed contamination of soil and surface water of the region with several persistent organic pesticides. The total OCPs level ranged from 0.36–104.50 ng g^–1 and 2.63–3.72 μg L^–1 in soil and surface water samples, respectively.     

The Status of Pesticide Residues in the Drinking Water Sources in Meiliangwan Bay, Taihu Lake of China

The study was carried out to assess the levels of pesticide residues in the water of Meiliangwan Bay, Taihu Lake of China. The most commonly employed organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs) and herbicide atrazine were analyzed. The water samples were collected seasonally from Meiliangwan Bay within a period of one year. The pesticides were analyzed by gas chromatography (GC) with μECD or NPD after solid-phase extraction (SPE), which was confirmed by GC with an ion trap mass spectrometry (MS). The mean concentrations were 1.98 ng/l for lindane, 0.378 ng/l for heptachlor epoxide, 0.367 ng/l for p,p′-DDE, 0.496 ng/l for p,p′-DDD, 1.06 ng/l for p,p′-DDT and 51.6 ng/l for dichlorvos, 39.0 ng/l for demeton, 346 ng/l for dimethoate, 4.12 ng/l for methyl parathion, 11.6 ng/l for malathion, 2.17 ng/l for parathion and 217 ng/l for atrazine. Generally, low concentrations of OCP were found, whereas the concentrations of the OPPs and atrazine in the water of Taihu Lake were relatively high. Heptachlor epoxide and lindane were the two most commonly encountered OCPs while dichlorvos, demeton and dimethoate were found to have much higher concentrations and occurrences than other OPPs.     

Status of insecticide contamination of soil and water in Haryana, India

Twelve samples each of soil and ground water were collected from paddy-wheat, paddy-cotton, sugarcane fields and tube wells from same or near by fields around Hisar, Haryana, India during 2002–2003 to monitor pesticide residues. Residues were estimated by GC-ECD and GC-NPD systems equipped with capillary columns for organochlorine, synthetic pyrethroid and organophosphate insecticides. In soil, HCH (0.002–0.051 μg g⁻¹), DDT (0.001–0.066 μg g⁻¹), endosulfan (0.002–0.039 μg g⁻¹) and chlordane (0.0002–0.019 μg g⁻¹) among organochlorines, cypermethrin (0.001–0.035 μg g⁻¹) and fenvalerate (0.001–0.022 μg g⁻¹) among synthetic pyrethroids and chlorpyriphos (0.002–0.172 μg g⁻¹), malathion (0.002–0.008 μg g⁻¹), quinalphos (0.001–0.010 μg g⁻¹) among organophosphates were detected. Dominant contaminants were DDT, cypermethrin and chlorpyriphos from the respective groups. In water samples, HCH, DDT, endosulfan and cypermethrin residues were observed frequently. Only chlorpyriphos among organophosphates was detected in 10 samples. On consideration of tube well water for drinking purpose, about 80% samples were found to contain residues above the regulatory limits.     

固相萃取- GC/MS法测定水中邻苯二甲酸酯类

采用固相萃取-GC／MS法测定水中6种邻苯二甲酸酯类有机污染物,比较了不同固相萃取柱对萃取效果的影响,优化了水样pH值、水样流量、穿透体积、洗脱溶剂、洗脱剂体积、洗脱流量等萃取条件。方法在0．050μg/L-800μg/L范围内线性良好,检出限为0．008μg/L～0．03μg／L,标准溶液测定的RSD≤10．5％,实际水样加标回收率为80．0％-100％。     

Investigation of heavy metal contaminations in the lower Sakarya river water and sediments

In this work, water and sediment samples were collected from three different stations located along the Sakarya river between May and September 2003. Lead, copper, chromium, zinc, nickel and cadmium concentrations were determined by using solvent extraction and flame atomic absorption spectrometric method. The results show that differences based upon sampling times, regions, sediment and water samples were observed. The mean levels of copper, nickel, chromium, lead, cadmium, zinc for sediment samples are; 4.630 μg g⁻¹, 13.520 μg g⁻¹, 8.780 μg g⁻¹, 2.550 μg g⁻¹, 9.990 μg g⁻¹ and for water samples are; 0.851 μg g⁻¹, 1.050 μg g⁻¹, 0.027 μg g⁻¹, 1.786 μg g⁻¹, 0.236 μg g⁻¹, 0.173 μg g⁻¹, respectively.     

固相萃取-高效液相色谱法测定废水中的酚类化合物

建立了Supelclean ENVI-Chrom P柱固相萃取-高效液相色谱法测定废水中11种酚类化合物的分析方法,并对固相萃取条件和液相色谱条件进行了讨论。该方法分离效果良好,净化效果明显,方法检出限为2×10-3~2×10-2mg/L,平行分析(n=6)的RSD为2.7%~16.4%,废水加标回收率除2,4-二硝基酚偏低以外,其他化合物的回收率为61.4%~115.8%。     

Fractionation and Sequential Extraction of Heavy Metals in the Soil of Scrapyard of Discarded Vehicles

Chemical and physical size fractionation of heavy metals were carried out on 20 soil samples from the scrap yard area. Tessier method was used in sequential extraction. Cadmium showed the highest levels among the other elements studied in the exchangeable fraction (about 33%), while other elements showed low levels in this fraction (≥1%). Lead and manganese were mostly found in the Fe–Mn oxide fraction, zinc and iron were mostly in residual fraction, while copper was mostly found in the organic fraction of the soil. Soil samples were size-fractionated into four sizes: 1000–500, 500–125, 125–53, and less than 53 μm. The highest levels of Fe, Cu, Pb, Mn, and Cd were found in the medium fraction (500–125 μm), while zinc showed its highest levels in the fine fraction (125–53 μm). The order of heavy metal load in the size fractions was found to be medium > fine > coarse > silt for Fe, Mn, Cu, Pb, and Cd, where it was found as fine > medium > coarse > silt for zinc.     

Heavy metal pollution in surface sediment and mussel samples in the Gulf of Gemlik

Different sources of pollution in Karasu Creek were investigated to obtain the water quality and ratio of contamination in this region. To achieve the main objectives of the present study, water samples were collected from Karasu Creek, starting from flow pattern at the upstream site of Akkaya Dam to the end of the dam, crossing the place where the Creek drains into. Dissolved oxygen, electrical conductivity, temperature and maximum/minimum pH were measured systematically for 12 months in the stations, where the water samples were collected. Chemical analyses of the water samples were carried out by using Cadas 50 S brand UV spectrometer to find out the Pb, Fe, Cu, Zn, Ni, Cr, Cd, S, F and Cn concentrations. These concentration were determined in μg/lt as 80–850; 180–4,920; 10–6,100; 440–25,530; 130–2,400; 120–280; 20–150; 214,250–1,113,580; 1,560–4,270 and 40–690, respectively. To determine metal levels of the water samples, multivariate analyses (element coefficient correlation, coefficient correlation dendrogram, hierarchical cluster analysis dendrogram, model summary and ANOVA) were used. The analyses yielded highly accurate results. There were positive correlations between some elements and their possible sources were the same. The stations which resembled each other along the creek were divided into three groups. The water quality of the creek was low and had toxic qualities. Eutrophication developed in Akkaya Dam along the creek. The source of pollution was thought to be industrial and residential wastes. Absolute (0–100 m), short distance (100–500 m) and medium distance (500–2,000 m) conservation areas should be determined in pollution areas along Karasu Creek and they should be improved.     

Sediment and Suspended Matter Lead Contamination in the Gulf of Kavala, Greece

Sediment and suspended particulate matter samples from 24 stations in the Gulf of Kavala have been examined for lead contamination. Grain size analysis and organic matter content were also performed. Total – anthropogenic sediment lead concentrations and enrichment factors at stations close to harbors and chemical industries were found higher (up to 209–135μg/g and 4.12 respectively), in relation to concentrations from the rest of the coastal zone. In the above areas, increased suspended particulate lead in the bottom of the water column was also recorded (up to 109μg/g). Total sediment lead concentrations composed of high natural Pb background increased with decreasing grain size, suggesting their association with the fine fractions of the sediments (31.1–66.0% mud presence) and the organic matter content (6–9% higher values). Overall, higher total lead concentrations in the sediments, determined by this work, appear to be significantly different from those reported for the Gulf of Kavala in previous studies and similar to those detected in other highly contaminated eastern Mediterranean coastal areas.     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

Risk Assessment of Organic Pesticides Pollution in Surface Water of Hangzhou

Advances in research on pollution of organic pesticides (OPs) in surface water, pollution survey and risk assessments of organochlorine pesticides (OCPs) and organophosphorus pesticides (OPPs) of surface water in Hangzhou are conducted. Total concentrations of dichloro-diphenyl-trichloroethane (DDT) and hexachloride-benzene (HCH) in surface water were observed to be 0–0.270 μg/L and 0–0.00625 μg/L respectively. DDE, as a metabolite of DDT and many species of OPP_S were determined in some samples of surface water. Parathion, the main pollutant among OPPs in surface water of Hangzhou, was observed to be 0–0.445 μg/L. Based on these experimental results, health risk assessments on the organic pollution are developed. It is observed that the total risk “R ^T” at present time of surface water in Hangzhou is mainly contributed by organophosphorus pesticides, especially Parathion; HCH and DDT are not the main contaminants; on the contrary, organophosphorous pesticides, especially Parathion, must be of concern at the present time.     

Spatial Variability and Monitoring of Pb Contamination of Farming Soils Affected by Industry

In this study, the relationship between some physico-chemical properties of soils and lead contamination in soil due to emission from industrial operations in Samsun province of Turkey was investigated. The extent of timely contamination was studied by comparing the obtained results with the results of the study conducted in the same region in 1998. An area of 225 km² (15 km × 15 km), which was divided into 1000 × 1000 m grid squares (16 lines in the east and south directions), was selected within the industrial area. The total of 256 grid points was obtained and soil samples were collected from three depths (0–5, 5–15, and 15–30 cm) of each grid center in 2004. The total Pb concentrations of soil samples were determined as 65.84–527.04 μg g⁻¹ at 0–5 cm in depth, 58.50 – 399.54 μg g⁻¹ at 5–15 cm in depth, and 44.65–330.07 μg g⁻¹ at 15–30 cm in depth. DTPA-extractable Pb concentrations of soils were found to be in the range of 1.52–9.03 μg g⁻¹, 0.54–7.09 μg g⁻¹, 0.19–6.13 μg g⁻¹ at 0–5, 5–15, and 15–30 cm depths, respectively. There were significant relationships between both total or DTPA-extractable Pb concentrations and selected physico-chemical properties of soil. According to enrichment factor (EF) values calculated from the total Pb concentrations, 11.3% of the study area (225 km²) was enriched with Pb in high level, but 77% of the area was in significant enrichment level with Pb. The average total and DTPA-extractable Pb concentrations increased as 11 and 13%, respectively in comparison with the results of 1998.     

Spatial and Temporal Variations in Trace Metal Concentrations in the Cockle, Austrovenus Stutchburyi from Otago, New Zealand

This is the first comprehensive study of sources of variation in metal concentrations within the whole tissues of a shallow burrowing, filter-feeding intertidal clam, Austrovenus stutchburyi. Samples were collected from 12 sites in April, August, November and February in 1993–1994 in the vicinity of Otago Harbour and Peninsula, New Zealand. Total tissue trace metal concentrations (μg g⁻¹ dry weight) were measured in individual animals for the essential metals : Mn, Cu, Zn, Ni and the non-essential Cr using trace-metal clean acid-digestion and ICP-OAES techniques. Average metal concentrations were 3–60 μg g⁻¹ for Cu, 40–118 μg g⁻¹ for Zn, 2–12 μg g⁻¹ for Mn, 5–35 μg g⁻¹ for Ni and 1–44 μg g⁻¹ for Cr. These levels decreased with body weight and differed amongst sites except for Cr in February (mid-summer). Highest concentrations occurred at sites close to a city (Dunedin) and within the central harbour region although the Cu, Zn, Ni and Cr concentrations did not correlate with the environmental gradient or season. At one coastal site, samples of both the blue mussel Mytilus galloprovincialis and cockles gave similar trends in trace metal levels. These results suggest that the cockle could be a useful trace metal biomonitor within NZ estuaries.     

Identification of Residues of Sulfosulfuron and its Metabolites in Subsoil-dissipation Kinetics and Factors Influencing the Stability and Degradation of Residues from Topsoil to Subsoil Under Predominant Cropping Conditions

Long term stability of sulfosulfuron was investigated in subsoil under the natural wheat cropping conditions. Experiments were conducted by applying a commercial formulation of sulfosulfuron on soil at 50 g/ha and 100 g/ha. To understand the factors influencing the persistence of residues two different experiments were conducted. In one experiment wheat crop was cultivated once at the beginning of the two years study period and subsequently the plots were kept undisturbed for the remaining period. In another experiment cultivation of subsequent crops were continued during the study period. In both the cases sulfosulfuron was applied only once at the beginning of the study. Representative soil samples were collected from the depths viz., 0–5, 15, 30, 45, 60 and 90 cm on different pre determined sampling occasions 50, 100, 200, 300, 400, 500 and 600 days after the application of the herbicide. The collected soil samples were analyzed for the residues of sulfosulfuron. Under the influence of continuous cropping conditions residues of sulfosulfuron were found to be relatively low when compared with the soil samples collected from the agriculture plots maintained without any cultivation. The residues detected are in the range 0.001 to 0.017 μg/g. Samples collected from the depth, at 30 to 45 cm showed higher residual concentrations. Soil samples were also showed the presence of break down products. The data has been confirmed by LC–MS/MS. The relation between residue content of sulfosulfuron and the factors contributing the stability of herbicide concentration were also studied.     

Concentrations of cadmium and lead heavy metals in Dardanelles seawater

Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10⁻⁵ M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l⁻¹ (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l⁻¹ (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.     

Distribution of heavy metals in the dissolved and suspended phase of the sea-surface microlayer, seawater column and in sediments of Singapore’s coastal environment

Concentrations of heavy metals were determined in the water column (including the sea-surface microlayer, subsurface, mid-depth and bottom water) and sediments from Singapore’s coastal environment. The concentration ranges for As, Cd, Cr, Cu, Ni, Pb and Zn in the seawater dissolved phase (DP) were 0.34–2.04, 0.013–0.109, 0.07–0.35, 0.23–1.16, 0.28–0.78, 0.009–0.062 and 0.97–3.66 μg L⁻¹ respectively. The ranges for Cd, Cr, Cu, Ni, Pb and Zn in the suspended particulate matter (SPM) were 0.16–0.73, 6.72–53.93, 12.87–118.29, 4.34–60.71, 1.10–6.08 and 43.09–370.49 μg g⁻¹, respectively. Heavy metal concentrations in sediments ranged between 0.054–0.217, 37.48–50.52, 6.30–21.01, 13.27–26.59, 24.14–37.28 and 48.20–62.36 μg g⁻¹ for Cd, Cr, Cu, Ni, Pb and Zn, respectively. The lowest concentrations of metals in the DP and SPM were most frequently found in the subsurface water while the highest concentrations were mostly observed in the SML and bottom water. Overall, heavy metals in both the dissolved and particulate fractions have depth profiles that show a decreasing trend of concentrations from the subsurface to the bottom water, indicating that the prevalence of metals is linked to the marine biological cycle. In comparison to data from Greece, Malaysia and USA, the levels of metals in the DP are considered to be low in Singapore. Higher concentrations of particulate metals were reported for the Northern Adriatic Sea and the Rhine/Meuse estuary in the Netherlands compared to values reported in this study. The marine sediments in Singapore are not heavily contaminated when compared to metal levels in marine sediments from other countries such as Thailand, Japan, Korea, Spain and China.