冷冻除脂-气相色谱-串联质谱法检测食用植物油中30 种多环芳烃

建立冷冻除脂--气相色谱-串联质谱检测食用植物油中30?种多环芳烃（polycyclic aromatic hydrocarbons,PAH）的方法。选用6?种氘标记PAH为内标,样品经乙腈--丙酮溶液（4∶1,V/V）于离心管中涡旋提取,10?000?r/min离心5?min,－80?℃对油脂冷冻固化,倾出提取液,再经减压浓缩和氮气吹干,以二氯甲烷复溶,气相色谱--串联质谱多反应监测方式进行检测。结果表明,在相应质量浓度范围内30?种PAH均有良好线性（R2＞0.998）,检出限为0.10～1.83?μg/kg,定量限为0.35～6.11?μg/kg,在5、20?μg/kg和50?μg/kg添加水平下的回收率为67.77%～119.28%,相对标准偏差为1.18%～12.47%。采用本方法对市售11?类38?个食用植物油样品的检测显示,萘、1-甲基萘、2--甲基萘、联苯、2,6--二甲基萘、苊烯、苊、2,3,6--三甲基萘、芴、二苯并噻吩、菲、蒽、1-甲基菲、荧蒽、芘、环戊烯[c,d]芘、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[e]芘和苯并[a]芘的检出率均为100%;5--甲基屈、苝、茚并[1,2,3--c,d]芘、二苯并[a,h]蒽、苯并[g,h,i]苝和二苯并[a,l]芘的检出率分别为86.84%、63.16%、81.58%、21.05%、81.58%和26.32%;二苯并[a,e]芘和二苯并[a,h]芘未检出;PAH总量为92.56～905.16?μg/kg,其中苯并[a]芘含量为1.94～7.40?μg/kg,依据食品安全标准限量,PAH处于较安全水平。     

熟化方式对酱卤风味牛肉品质及多环芳烃含量的影响

比较蒸制、煮制、炸制、煎制、烤制和微波6 种熟化方式对酱卤风味牛肉品质（感官评分、色泽、质构、水分含量、pH值、脂肪氧化）和化学危害物多环芳烃（polycyclic aromatic hydrocarbons,PAHs）含量的影响。结果表明：烤制、蒸制、煮制熟化酱卤风味牛肉色泽品质较好;烤制、煎制和炸制熟化酱卤风味牛肉水分含量偏低,且与其他组有显著差异（P＜0.05）;蒸制熟化酱卤风味牛肉很好地保持了水分含量,具有较好的质构特性;烤制、炸制熟化酱卤风味牛肉的脂肪氧化程度偏高（P＜0.05）,而蒸制熟化酱卤风味牛肉的脂肪氧化程度最低;与其他熟化方式相比,蒸制熟化酱卤风味牛肉的感官评分较高;烤制、煎制、炸制熟化酱卤风味牛肉中苯并(a)芘、苯并(a)蒽、苯并(b)荧蒽及?4 种PAHs的总含量均高于7.0 μg/kg,蒸制、微波熟化组约为3.1 μg/kg。综合评估得出,蒸制是一种有效的酱卤风味牛肉熟化加工方式,牛肉品质与传统卤煮牛肉更为接近。     

高效液相色谱-荧光检测法检测植物性食品中14种欧盟优控多环芳烃

目的 建立准确测定蔬菜、水果及粮食中多环芳烃含量,了解河北省内上述食品中14种欧盟优控多环芳烃(苯并(c)芴、苯并(a)蒽、?、5-甲基?、苯并(j)荧蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,l)芘、二苯并(a, h)蒽、苯并(g,h,i)苝、茚并(1,2,3-cd)(a)芘、二苯并(a,e)芘、二苯并(a,i)芘、二苯并(a,h)芘)的实际污染状况。方法 样品经环己烷：乙酸乙酯(1:1, V:V)溶液超声提取后,浓缩至近干,经正己烷复溶后通过多环芳烃专用固相萃取柱进行净化处理,洗脱液经浓缩后用乙腈定容,采用液相色谱-荧光检测法进行检测。结果 14种化合物的线性范围为1.00~18.0μg/kg;方法回收率为60.9%~125.4%,相对标准偏差为2.2%~7.6%;苯并(c)芴、苯并(a)蒽、?、5-甲基-1,2-苯并菲、苯并(j)荧蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,e)芘、二苯并(a,i)芘、二苯并(a,h)芘检出限为0.15μg/kg;二苯并(a,l)芘、二苯并(a, h)蒽、苯并(g,h,i)苝、茚并(1,2,3-cd)芘检出限为0.3μg/kg。市售的96份样品中, 检出不同种类不同含量的多环芳烃类化合物, 检出率为51.0%。结论 本方法重现性好,检测灵敏度高,可用于水果、蔬菜及粮食中14种多环芳烃的检测。     

高温处理对羊肉中主要有害物质的影响

为研究煎、炸、烤3种高温处理对羊肉中有害物质的影响,试验选用横山羊肉,通过调控其高温处理时间和温度,采用分光光度法、气相色谱-质谱(GC-MS)外标法和高效液相色谱(HPLC)外标法分别测定高温处理后羊肉中的亚硝酸盐、反式油酸(C18:1 trans-9)及多环芳烃(PAHs)。结果表明:煎制2 min和3 min处理的羊肉中亚硝酸盐含量较低(p0.05);处理时长对C18:1 trans-9含量影响差异不显著(p0.05);2 min和3 min处理的羊肉中菲、芘和二苯并[a,h]蒽含量均较低(p0.05);炸制3 min处理的羊肉中亚硝酸盐,C18:1 trans-9,芘、苯并[k]荧蒽、苯并[a]芘和二苯并[a,h]蒽、苯并[a]蒽5种PAHs含量均最低(p0.05);160℃烤制处理的羊肉中亚硝酸盐含量最低(p0.05);160℃和180℃处理的羊肉中C18:1 trans-9含量较低(p0.05);160℃处理的羊肉中萘、菲和苯并[a]芘含量低于180℃,菲、苣、苯并[k]荧蒽和苯并[a]芘含量低于200℃(p0.05)。综合分析,3种高温处理对羊肉中有害物质有较大影响,羊肉在226～228℃下煎制2～3 min、炸制3 min、在160℃下烤制40 min时3类有害物质含量相对较低。     

不同工艺即食烤鱼多环芳烃检测方法及变化研究

目的:建立即食烤鱼16种多环芳烃（Polycyclic aromatic hydrocarbons, PAHs）检测方法,分析不同工艺对烤鱼PAHs种类及含量的影响。方法:样品经正己烷提取,采用固相萃取柱净化,二氯甲烷洗脱,高效液相色谱法测定。结果:16种PAH_S相关系数为0.9993~0.9998,检出限为0.20~2.50 μg/kg;加标回收率为64.25%~122.8%,相对标准偏差为1.38%~7.13%。在碳烤、油炸、电烤三种不同熟化方式下,烤鱼中调味料的添加可减少PAHs的生成量;烤鱼中PAHs的种类和含量为碳烤>油炸>电烤,样品中萘、苊烯、菲和芘检出含量较高,碳烤样品PAHs总量高达58.74 μg/kg,明显高于油炸和电烤样品组;熟化时间和温度对烤鱼PAHs种类及含量均有影响,随油炸时间延长、油炸温度增高,样品PAHs检出种类和含量增加明显,其中,萘、苊烯、菲、荧蒽和芘含量增高达3~5倍;随电烤时间和温度的增加,样品中PAHs种类增多,PAHs总量亦提高;通过风险评估,烤鱼加热时间控制在6 min,温度200 ℃以内,摄入频率小于每月2次,食用风险低。结论:建立了烤鱼中16种PAHs的检测方法;进行了不同工艺烤鱼样品中PAHs的种类、含量变化分析及风险评估,为即食烤鱼熟化工艺选择提供依据。     

我国主产区油茶持久性有机污染物分布特征及相关性研究

为了明确油茶中持久性有机污染物(POPs)的污染分布特征,利用气相色谱-三重四极杆串联质谱(GC-MS/MS)对我国主产区45个采样点135批次油茶果不同部位及对应油茶林土壤进行16种多环芳烃(PAHs)、18种多氯联苯(PCBs)和21种有机氯(OCPs)污染水平分析。同时分析油茶籽仁和油茶林土壤中主要POPs之间相关性。结果表明:油茶果各部位及油茶林土壤PAHs污染以萘、苊烯、苊萘嵌戊烷、荧蒽等低环PAHs污染较为明显;PCBs污染程度很轻,含量均在1μg/kg以下;OCPs污染主要为狄氏剂、毒杀芬、α-六六六、硫丹、异狄氏剂和艾氏剂。油茶籽仁中荧蒽与菲具有强正相关(R~2=0.90);油茶林土壤中芴与菲,■与苯并(a)蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘和苯并(a)蒽,PCB138与茚并(1,2,3-cd)芘,PCB180与苯并(g,h,i)苝,p,p′-DDE与o,p′-DDT、p,p′-DDD之间均具有较强相关性(R~2=0.81～0.98)。     

食用植物油中多环芳烃含量水平调查分析

调查了8类、116个食用植物油样品中的苯并(a)蒽、■、苯并(b)荧蒽和苯并(a)芘的污染情况。采用简单的液-液萃取法进行前处理,GC-MS/MS测定。结果表明:不同品种食用植物油多环芳烃含量差异较大;苯并(a)芘的检出率为85.34%,检出结果范围为0.59~9.75μg/kg;4种多环芳烃总量的检出率为100%,检出结果范围为0.88~59.17μg/kg;苯并(a)芘含量与4种多环芳烃总量成线性关系。     

GC-MS法测定多种食用油中的多环芳烃

多环芳烃是一类常见的环境有机污染物,随着人们对其毒性研究逐步深入,各国相继制定限量要求。随机选取市面上不同种类的食用油,采用GC-MS法进行多环芳烃的测定,评估其食品安全风险。结果表明, 15种食用油中苯并[a]芘含量在0.00～9.20μg/kg之间,苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲的含量之和在0.00～28.74μg/kg之间, 16种多环芳烃总量在0.00～72.47μg/kg之间。对随机网上购买食品安全风险较高的10份芝麻油进行测定,苯并[a]芘含量在0.00～6.76μg/kg之间,苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲的总量在0.00～9.64μg/kg之间,16种多环芳烃总量在0.00～16.18μg/kg之间。植物油中多环芳烃含量水平相差较大,部分存在一定的食品安全风险,出口企业还应关注苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲含量的水平。     

油脂煎炸过程中多环芳烃含量的变化

对大豆油、米糠油和棕榈油进行油条煎炸试验,之后对不同煎炸时间油脂中多环芳烃含量进行检测分析,研究煎炸时间对油脂中多环芳烃含量的影响。结果表明:随着煎炸时间的延长,3种油脂中Bap、PAH4、PAH16的含量都呈现明显上升趋势。在32 h的煎炸过程中,大豆油Bap、PAH4、PAH16的含量(μg/kg)分别从原油的1.58、6.88、18.73增加至3.93、10.35;56.10,米糠油Bap、PAH4、PAH16的含量分别从原油的2.52、6.50、25.53增加至3.10、10.34、100.71;棕榈油Bap、PAH4、PAH16的含量分别从原油的1.67、8.60、25.23增加至2.26、10.95、59.98。在高温煎炸过程中,多环芳烃各组分含量的增幅是不同的。大豆油中增幅最大的组分是苊,增幅最小的是苯并(b)荧蒽;米糠油中增幅最大的也是苊,增幅最小的是苯并(g,h,i)苝;棕榈油中增幅最大的是芴,增幅最小的是苯并(a)蒽;3种油脂中轻质多环芳烃含量及增幅都要远多于重质多环芳烃。     

天然维生素E油中PAH4连续脱除工艺研究北大核心CSCD

建立了一种天然维生素E油连续通过颗粒活性炭的固定床吸附工艺,从而实现有效脱除其中含有的微量多环芳烃(PAHs)。通过单因素实验分别考察了料液比、体系温度、物料在填料中的吸附时间对PAH4(苯并(a)芘、苯并(a)蒽、苯并(b)荧蒽、䓛)脱除效果的影响,并通过正交实验进行了工艺条件优化。同时,考察了PAH4脱除过程对天然维生素E含量的影响。结果表明:以95%乙醇为溶剂,料液比(天然维生素E油与溶剂比)1∶3,体系温度40℃,在以颗粒活性炭为填料的固定床内吸附4 h的条件下,可使天然维生素E油中PAH4的残留量降至7.3μg/kg(其中苯并(a)芘含量为1.8μg/kg),符合欧盟标准要求的苯并(a)芘含量小于或等于2μg/kg,PAH4含量小于或等于10μg/kg的限量标准,且采用该PAH4脱除工艺后维生素E的含量没有受到明显影响。     

Polycyclic aromatic hydrocarbons (PAHs) in yerba mate (Ilex paraguariensis) from the Argentinean market

Polycyclic aromatic hydrocarbons (PAHs) occurrence in 50 samples marketed in the main supermarkets from Argentina was surveyed. A high performance liquid chromatography (HPLC) method was applied with fluorescence detection (FLD) and UV—VIS diodes array detector (DAD) for the analysis of 16 PAHs in “yerba mate” (Ilex paraguariensis), with recoveries higher than 89% and limits of detection and quantification lower than that found by other methodologies in previous studies. Contamination expressed as the sum of 16 analysed PAHs ranged between 224.6 and 4449.5 μg kg^?1 on dry mass. The contamination expressed as PAH4 (sum of benzo(a)pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene) varied between 8.3 and 512.4 μg kg^?1. The correlation coefficient for PAH2 (sum of benzo(a)pyrene and chrysene) and PAH4 groups was 0.99, for PAH2 and PAH8 (sum of benzo(a)pyrene, chrysene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i)perylene, dibenzo(a,h)anthracene and indeno(1,2,3cd) pyrene) 0.97 and for PAH4 and PAH8 0.98.     

Trophic dilution of polycyclic aromatic hydrocarbons (PAHs) in a marine food web from Bohai Bay, north China

Trophic transfer of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems is an important criterion for assessing their ecological risk. This study analyzed 18 PAHs in phytoplankton/seston, zooplankton, five invertebrate species, five fish species, and one seabird species collected from Bohai Bay, and trophic transfer of the PAHs was determined in the food web, of which the length was approximately 4 on the basis of stable nitrogen isotope values. The concentrations of PAHs (2-64.5 ng/g wet weight) in the marine ecosystem were moderate compared with other marine organisms worldwide, and the PAH compositions exhibited species-specific profiles that were related to trophic levels in some organisms. Significant negative relationships were also found between trophic levels and lipid-normalized concentrations for 10 PAH compounds (acenaphthylene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene + benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and perylene), and their trophic magnification factors (TMFs) ranged from 0.11 for fluoranthene to 0.45 for acenaphthylene. These results confirm that PAHs undergo trophic dilution in the marine food web, which is likely to be the combined results of low assimilation efficiencies and efficient metabolic transformation at higher trophic levels.     

Effects of grilling and roasting on the levels of polycyclic aromatic hydrocarbons in beef and pork

The concentrations of seven polycyclic aromatic hydrocarbons (PAHs) viz. chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene, and indeno(1,2,3-c,d)pyrene in 150 samples of commercial meat products were determined. The PAHs were extracted with hexane, purified with Sep-Pak Florisil cartridges and determined by high-performance liquid chromatography using a fluorescence detector. Levels of PAHs were dependent on the method of cooking and type of heat source used. Relatively high levels of PAHs, 10.2 μg/kg on average, were found in charcoal-grilled pork samples. Average PAH levels in beef did not exceed 0.80 μg/kg. Charcoal grilling of pork samples resulted in extremely high levels of benzo(a)pyrene (3.0 μg/kg), while the average benzo(a)pyrene levels in charcoal-grilled beef samples were 0.15 μg/kg. These data can be used to estimate the dietary exposure of consumers to PAHs and to assess any potential risk associated with the ingestion of these foods.     

Polycyclic aromatic hydrocarbons in fresh and cold-smoked Atlantic salmon fillets

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in smoked fish as a consequence of cold smoking was studied. Raw fillets of Salmo salar from Norway or the Irish Sea were sampled in a modern smokehouse and examined for PAH content. The same fillets, labeled with an identification number, were sampled immediately after the smoking process and analyzed. Among the investigated compounds, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, and benzo[ghi]perylene were detected in both raw and smoked fillets. No significant difference (P < 0.01) was observed between raw and smoked samples in the concentrations of six PAHs, but significant differences were found for fluorene, anthracene, fluoranthene, benz[a]anthracene, and benzo[ghi]perylene. Results confirm that PAHs concentrations in smoked fish are the product of both sea pollution and the smoking process. A modern smoking plant with an external smoke generator and a mild treatment as described here will not add significantly to the concentration of PAHs, except for some compounds.     

Exposure to polycyclic aromatic hydrocarbons through consumption of edible marine species in Catalonia, Spain

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs; naphthalene, acenaphtylene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-c,d]pyrene, dibenzo[a,h]anthracene, and benzo[g,h,i]perylene) were determined by gas chromatography-mass spectrometry in samples of 14 edible marine species (sardine, tuna, anchovy, mackerel, swordfish, salmon, hake, red mullet, sole, cuttlefish, squid, clam, mussel, and shrimp) collected in March and April 2005. These species are widely consumed by the population of Catalonia, Spain. PAH intake was also estimated for eight age and sex groups of this population. Mussel, clam, and shrimp had the highest PAH concentrations (22.4, 21.5, and 15.9 ng/g of fresh weight, respectively). In contrast, sole (2.5 ng/g of fresh weight) and cuttlefish and squid (both 3.0 ng/g of fresh weight) had the lowest mean concentrations. The highest PAH intake was found in women and girls (5.3 and 5.2 ng/kg/day, respectively), but female adolescents and female seniors had the lowest PAH intakes (3.3 ng/kg/day in both groups). The intake of benzo[a]pyrene and six other PAHs that are probably human carcinogens through consumption of these marine species would be associated with 0.27/10(6) increase in the risk of development of cancer over a 70-year life span.     

Polycyclic aromatic hydrocarbons (PAH) in chocolate on the German market

Benzo[a]anthracene (BaA), chrysene (CHR), cyclopenta[c,d]pyrene (CPP), 5-methylchrysene (5MC), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[j]fluGoranthene (BjF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DhA), indeno[1,2,3-cd]pyrene (IcP), benzo[g,h,i]perylene (BgP), dibenzo[a,l]pyrene (DlP), dibenzo[a,e]pyrene (DeP), dibenzo[a,i]pyrene (DiP) and dibenzo[a,h]pyrene (DhP), the 15 SCFPAH, assessed to be relevant as well as benzo[c]fluorene (BcL) recommended by the European Food Safety Authority (EFSA), were analysed in different types of chocolate. The sample preparation included accelerated solvent extraction (ASE), size exclusion chromatography (SEC) and solid phase chromatography using small silica gel columns. The individual PAH were separated by gas chromatography using a VF-17ms GC column and detected by high resolution mass spectrometry (HRMS). The investigation of 40 samples of various types of chocolate with different cocoa contents resulted in a median benzo[a]pyrene (BaP) content of 0.22 μg/kg. Furthermore, the results showed a linear correlation between the content of BaP and the sum content of the 16 priority PAH. Therefore, the analysis of BaP as a leading substance seems to be suitable to estimate the PAH contamination in chocolate.     

Determination of polycyclic aromatic hydrocarbons in smoked fishery products from different smoking kilns

The levels of 13 polycyclic aromatic hydrocarbons (PAH) were determined by an HPLC method with fluorescence and UV detection and by a GC/MS technique in smoked fishery products from modern smoking kilns with external smoke generation and from traditional smoking kilns. The average benzo(a)pyrene (BaP) concentration of all 35 samples from commercial smoking kilns with external smoke generation was 0.1 g/kg (wet weight) and the sum of the carcinogenic compounds determined in the study, i.e. benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene and indeno(1,2,3-c,d)pyrene did not exceed 4.5 g/kg (wet weight). The BaP levels of the 27 smoked fish samples from traditional kilns ranged from 0.2 g/kg to 4.1 g/kg, with a mean value of 1.2 g BaP/kg. The average concentration of the sum of the carcinogenic compounds was 9.0 g/kg. Large variations were found in the content of the non-carcinogenic PAHs phenanthrene, anthracene, fluoranthene and pyrene in all samples from both types of smoking kilns.     

Assessment of the dietary habits and polycyclic aromatic hydrocarbon exposure in primary school children

Thirty Italian children, 7–9 year aged, living in Naples were investigated on their dietary habits and on polycyclic aromatic hydrocarbon (PAH) exposure by a food diary-questionnaire and one week duplicate diet sample analyses. Daily total food consumption mean value was 632 ± 215 g day^?1, median value 613 g day^?1. The daily energy intake and the diet composition meanly agreed with the official guidelines for the Italian children. Sixteen PAHs were simultaneously detected and, according to the European Food Safety Authority (EFSA) approach, benzo[a]pyrene; benzo[a]pyrene + chrysene (PAH2); PAH2 + benz[a]anthracene + benzo[b]fluoranthene (PAH4); PAH4 + benzo[k]fluoranthene + benzo[ghi]perylene + dibenz[a, h]anthracene + indeno[1,2,3-cd]pyrene (PAH8) were considered in evaluating the children's dietary exposure to PAHs. The benzo[a]pyrene (BaP) median concentrations in foods varied from 0.06 to 0.33 µg kg^?1. Only three samples of cooked foods (one fish and two meat samples) exceeded legal limits fixed by the European Union for BaP. Daily median intakes of benzo[a]pyrene, PAH2, PAH4, and PAH8 were 153; 318; 990; 1776 ng day^?1; their median exposure values were 5; 10; 28; 54 ng kg^?1 bw day^?1. The Margins of Exposure (MOEs) in median consumers agreed with the EFSA safety values except for PAH8.     

Influence of collagen and natural casings on the polycyclic aromatic hydrocarbons in traditional dry fermented sausage (Petrovská klobása) from Serbia

The aim of this study was to determine the content of polycyclic aromatic hydrocarbons—PAHs (acenaphthylene, anthracene, fluorene, phenanthrene, pyrene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, chrysene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene, and benzo[ghi]perylene)—from Environmental Protection Agency list (United States Environmental Protection Agency) in traditional dry fermented sausage (Petrovská klobása) stuffed in collagen (C) and natural casings (N). Benzo[a]pyrene as well as PAH4 (benz[a]anthracene, benzo[b]fluoranthene, benzo[a]pyrene, and chrysene) were not detected in all examined samples. Results obtained in this study indicated that at the end of drying, as well as at the end of storage period, total content of 13 US-EPA PAH was significantly (P < 0.05) lower in sausages with collagen casing (56.2 and 73.6 μg/kg, respectively) than in sausages with natural casing (137.1 and 206.2 μg/kg, respectively).